A Users Guide to ZINDO -- a Comprehensive Semi-Empirical SCF/CI Package. This is one of the most versatile SCF/CI programs available and as a consequence, it has a great number of options. It can perform PPP, EHT, IEHT, CNDO and INDO type calculations. This handout is a (hopefully) straightforward guide to using this program. If you have any suggestions on how to make this handout more understandable, please feel free to contact any of the authors listed below. Closed shell CNDO program M. Zerner and C. Warren Uppsala 1969 Closed shell INDO program M.C. Zerner and J.E. Ridley Guelph 1972 Open shell UHF INDO program M.C. Zerner and A.D. Bacon Guelph 1975 Transition metal parameterization M.C. Zerner and R.F. Kirchner Stanford 1977 Open shell restricted Hartree-Fock Guelph 1980 M.C Zerner and W. D. Edwards Rumer diagram CI 1980 M.C. Zerner , J. McKelvey and W.D. Edwards Guelph Taken in part from D.D. Shillady VCU Localization 1984 J.C. Culberson and M.C. Zerner Florida Taken in part from W. Luken and J.C. Culberson Duke Geometry Optimization 1985 J.D. Head, M.C. Zerner, B. Weiner Guelph and Florida Fragment Orbitals, Namelist Input 1986 A.D. Cameron, M.C.Zerner Florida Spin Orbit Treatment M. Kotzian, N. Roesch and M C. Zerner Munich 1991 Rumer Treatment Polarizabilities Bill Parkinson, Jenwei Yu and M. C. Zerner Florida 1986-1996 Spin-Orbit treatment M.Kotzian, N.Roesch,R.Pitzer,M.C.Zerner Munich Double group treatment and Florida 1989 Projected UHF Florida 1995 M. Cory and M. C. Zerner Solvent Effects Tartu and Florida 1991-1996 Toomas Tamm, Mati Karelson and M.C. Zerner -------------------------------------------------------------------- ---- Contents ------------------------------------------------------ -------------------------------------------------------------------- 1. References 2. Introduction 3. Section I : Closed shell ground state scf Section II : Open shell (uhf) scf Section III : Configuration Interaction Section IV : Geometry optimization Section V : Electron assignment Section VI : Calculation of polarizabilities Section VII : Spin-orbit calculation Section VIII: Power users - Print options - Vectors - Electrostatic potentials - Triplet parametrization - Configuration mixing for metals - Point charges - Polarizabilities - Self consistent reaction field - Resonance Integrals - Localization - Fragment orbitals - Memory Management - Historical switches - Self Consistent Field Convergence 4. Some program arrays 5. File structure 6. Control words and data blocks -------------------------------------------------------------------- -------------------------------------------------------------------- ---- References: --------------------------------------------------- -------------------------------------------------------------------- Pople,Santry,Segal.............J. Chem. Phys., 43, S129,(1965) Pople,Segal....................J. Chem. Phys., 43, S136,(1965) Pople,Segal....................J. Chem. Phys., 44, 3289,(1966) Santry,Segal ...............J. Chem. Phys., 47, 158,(1967) Santry.........................J. Amer. Chem. Soc., 90,13,(1968) Ridley,Zerner ................Theoret. Chim. Acta, 32,111,(1973) Ridley,Zerner .................Theoret. Chim. Acta, 42,223(1976) Bacon,Zerner .................Theoret. Chim. Acta, 53,21 (1979) Zerner,Loew,Kirchner,Mueller-Westerhoff .................J. Amer. Chem. Soc., 102,589(1980) Head,Zerner .................Chem. Phys. Lett., 122,264(1985) Head,Zerner .................Chem. Phys. Lett., 131,359(1986) Anderson,Edwards,Zerner........Inorg. Chem., 25,2728(1986) Edwards,Zerner.................Theoret. Chim. Acta, 72,347(1987) Kotzian, Roesch,Zerner.........Theoret. Chim. Acta, 81,201(1992) .........Intern. J. Quant. Chem, S25,545(1991) -------------------------------------------------------------------- ---- INTRODUCTION: ------------------------------------------------- -------------------------------------------------------------------- The ZINDO program has, at its heart, two different semi-empirical procedures: a method for calculating spectroscopic properties (spectroscopic gammas) and a method for calculating geometries (theoretical gammas). Each has a different set of options, and consequently it is important that you decide what sort of calculation you want to perform. For example, if you want charge distributions, dipole moments or orbital energies, you should use spectroscopic gammas. If you want relative energies of ground state molecules, you should use theoretical gammas. Geometry optimization MUST be done with theoretical gammas. Configuration Interaction SHOULD be done with spectroscopic gammas in order to obtain the best electronic spectroscopic predictions. In all cases, the input file will consist of at least 3 sections: $TITLEI, $CONTRL and $DATAIN. The data fields for the $CONTRL section is free format, namelist type input. This means that the value of variables, switches and arrays needed to run the program can be read in, by name, in random order and in a nearly arbitrary format. All that is required is a valid name, followed by an equal sign (may be omitted for backwards compatibility, but such omission may not be supported in the future), then followed by one or more values. Comments begin with an ! (exclaimation point) and continue until the end of the line. Comments may be included anywhere in the file. Some data blocks require FORMATted data in a specific order, but the sections themselves may appear in any order. The section names must contain a $ sign in column 2, immediately followed by the name of the section (upper or lower case). Each section ends with a similar line containing $END . Arrays can be assigned on element-by-element basis, e.g. A(1)=4 a(4)=10 a(2)=9, or in longer sections. The index of the first element must always be provided: a(1)=4 9 0 10 . If the first method is used, the skipped index numbers will remain at default values. Some sections, $CONTRL in particular, allow the actual input to be placed on the same line, but since this is not universal (yet). For example, the following input would be valid: $contrl scftyp=uhf $end You may have several similar sections in the same file, and you will be able to choose between them by shifting the section name out of column 2. In the following example, the first input is ignored, but the second one is processed: $contrl scftyp=rhf $end $contrl scftyp=uhf $end The following examples illustrate the input required for a number of common cases. -------------------------------------------------------------------- ---- Section I: Closed shell ground state scf ---------------------- -------------------------------------------------------------------- $TITLEI Make-believe water calculation used as an illustrative example 20 June, 1988. The title can be as long as you wish. Updated, TT, 28 May 1996. $END $CONTRL SCFTYP = RHF RUNTYP = ENERGY ENTTYP = COORD UNITS = ANGS ASYM = C2V ! ***** Base name for temporary and output files ***** ONAME = water NEL = 8 MULT = 1 ITMAX = 20 SCFTOL = 0.000010 APX = INDO/1 INTTYP = 1 INTFA(1) = 1.000000 1.267000 0.585000 1.000000 1.000000 $END $DATAIN 0.000000 0.000000 0.000000 8 0.000000 1.000000 -1.000000 1 0.000000 -1.000000 -1.000000 1 $END ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: Input for CLOSED SHELL GROUND STATE WATER Explained ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: $TITLEI The title can be anything you wish and as long as you wish. $END ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: $CONTRL section The first five variables determine the type of calculation and the nature of the input. SCFTYP = RHF <----- a standard closed shell RHF type calculation = UHF ----- an Unrestricted HF type calculation = UHFA ----- a UHF calculation followed by annihilation of the next higher spin component = PUHF ----- a UHF calculation followed by projecting out the pure S=Ms densities. An analysis of the higher spin components, i.e. S > Ms, contributions to the unprojected wavefunction is also performed. TO calculate the Mulliken Population for each component, place PUHF_MULPOP in the $OUTPUT block. The number of multiplets that are considered can be limited by PUHFST in the $CONTROL block. PUHFST = 0 is the default, and all components of the UHF wavefunction are analyzed from M = Sz to M = NEL/2, or until the weight of a multiplet is below an internal threshold, now 10**(-8). Else: PUHFST=ABCD where ABCD is a four character integer, it should be viewed as two contiguous I2 words. Depending what PUHFST is yields varying results, e.g. 0103 = 103 = 0301 = 301 would report the energies for the first three spin-components. (There is no case for which the weights of all components are not reported.) In addition, if PUHF_MULPOP is also set then the Mulliken populations of the three spin states will also be reported. If PHUFST=2=02 is given, then only the energy of the second component is given, and only it's Mulliken population analysis if PUHF_MULPOP is also set. If PUHFST=-1 then only the weights are reported, and if PUHF_MULPOP is set then the mull. pop.s for all reported weights = ROHF ----- a spin restricted open shell RHF calculation. This option requires additional input! = SUHF ----- This is a UHF calculation with laGrange constraint that the multiplicity be MULT, M -> Sz. The Langrange constraint LAMBDA = X may be given in the $CONTRL block. The default is LAMBDA = 0.2 . See N. Handy. For large enough LAMBDA this approaches the ROHF solution, but convergence is slow for large LAMBDA. RUNTYP = ENERGY <----- a simple SCF calculation = GEOM ----- a geometry optimization calculation = CI ----- a configuration interaction calculation = CIF ----- if not a Rumer CI, see below, this keyword will save considerable memory. = RPA ----- an RPA calculation will be set up as a separate job. See ZINDORPA.HLP. The operation requires pgm rpago with input ONAME_rpa.DAT and generates output ONAME_rpa.out, i.e., rpago < ONAME_rpa.DAT. = SELFEN ----- Calculates the ionisation spectrum from the electron propagator Formalism. Several files are created ONAME_sel.xxx. Although these are kept, they can be deleted unless a restart option is used. ENTTYP = COORD <----- atomic positions in cartesian coordinates = ZMAT <----- atomic positions in internal coordinates = PDB <----- protein data base input UNITS = ANGS <----- cartesian coordinates in units of angstrom = BOHR ----- cartesian coordinates in units of bohrs = CANGS <----- cartesian coordinates in units of angstrom center the coordinates, and rotate to principle moments of inertia = CBOHR <----- cartesian coordinates in units of bohrs center the coordinates, and rotate to principle moments of inertia ASYM = C2V <----- Point group is C2V. Other possibilities include = C2 the following Abelian groups. In all cases, the = CI C2 axis must lie along the z axis of the molecul = CH = C2H = D2 = D2H NOTE. If in the $CONTRL block DETSYM = 1, the program will determine molecular symmetry Output File Name ONAME = ANYNAME ----- This 8 character name will be used to generate filenames used by the program. Switches NAT = 3 ----- Number of atoms (usually omitted). This must be equal to the actual number of atoms in $DATAIN. NEL = 8 ----- Number of valence electrons (or CHARGE = 0.0) --- will generate 8 electrons MULT = 1 ----- Multiplicity (number of unpaired electrons + 1) ITMAX = 20 ----- Maximum number of SCF cycles. This depends on the size and complexity of the problem. 20 is usually enough for most moderate size problems. SCFTOL = 0.0001 ----- Convergence criteria for the diagonal of the density (bond orders). If differences between densities from one cycle to the next are all less than this, convergence is assumed. Program will print the message: SENSE LIGHT 2 IS ON APX = EHT -- Extended Huckel ITMAX > 0 iterative Extended Huckel CNDO/1 CNDO/2 INDO/1 <<<<< (default) Method of choice (author's favorite) INDO/2 NDDO/1 NDDO/2 PPP theory The following is supported for compatibility: IAPX = 0 : Extended Huckel 1 : CNDO/1 2 : CNDO/2 3 : INDO/1 (default) 4 : INDO/2 5 : NDDO/1 6 : NDDO/2 7 : PPP INTTYP = 0 <<<<<< Theoretical (Fo) Gammas (GEOMETRY theory) The higher Slater Condon Factors are semi-empirical or they are scaled calculated = 1 <<<<<< Mataga-Nishimoto Gammas (SPECTROSCOPIC theory) = 2 ----- Not presently used = 3 ----- Ohno-Klopman Gammas (CNDO/INDO/PPP only) = 4 ----- Pariser-Parr Gammas = 5 ----- Modified Warshel Gammas = -1 ----- All Integrals ab-initio Interaction factors INTFA(1) = S-sigma, P-sigma, P-pi, D-sigma, D-pi, D-delta For spectroscopic singlet-recommended for nearly ALL cases (especially for calculations for UV/visible spectra) INTFA(1) = 1.0 1.267 0.585 1.0 1.0 1.0 For ordinary CNDO or INDO-recommended for geometry optimisation INTFA(1) = 1.0 1.0 1.0 1.0 1.0 1.0 For EHT (Hoffmann recommends factors of 1.75) INTFA(1) = 1.89 1.89 1.89 1.89 1.89 1.89 For PPP INTFA(1) = 0.585 0.585 0.585 0.585 0.585 0.585 $END ----- Other switches and parameters can go in this section See power users section (section VI) for more information ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: $DATAIN section: Atomic coordinates and atomic numbers One line for each atom or centre. Comments are allowed anywhere; they start with an exclamantion mark and continue through end of line. The first line which is blank (not a comment and no coordinates), or which contains the string '$END', signals the end of input. There are several options in which to enter the atomic information: METHOD 1: The traditional XYZ coordinates. Free format. The first four -------- fields (X,Y,Z,atomic number) are required, others are optional, but quantum numbers and exponents must appear in pairs as explained below: X Y Z Atomic Number Net Valence Charge Basis Set Exponent X Y Z ----- Cartesian coordinates for each atom in units specified in variable UNITS Atomic Number ----- Integer Net Valence Charge = 4.0 for neutral carbon = 8.0 for neutral Fe = 0.0 for DEFAULT values (omit if default and no exponents are input) For PPP calculations *** INPUT IS REQUIRED *** = 1.0 for C = 1.0 for N (PYRIDINE) = 2.0 for N (PYRROLE) Basis set definition = 1 for S = 2 for S,P = 3 for nS,nP,nD = 4 for nS,nP,(n-1)D = 5 for ns, np,(n-1)d,(n-2)f = 6 to be continued = 0 for DEFAULT Exponents can be overridden (omit for defaults): n, Exponent(S); n, Exponent(P); n, Exponent(D) n is the principle quantum number for the orbital EXAMPLES: --------- Oxygen atom, all defaults 0.000000 0.000000 0.000000 8 This is the same as: 0.000000 0.000000 0.000000 8 6.000000 2 Carbon atom, reset exponents 0.000000 0.000000 0.000000 6 4.000000 2 2 1.7000 2 1.7000 Point charge 0.000000 0.000000 0.000000 0 -0.500000 $END METHOD 2: Re-defining atomic types using TABS: -------- Input X, Y, Z, atomic number as above, then add END or TABxx to the end of the line. IF END, all information is defaulted as in the very first example above. If TAB, you will need to add a $TABS input block, which defines atomic types, distinhuished by the two characters immediately following 'TAB': 1.11111111 1.23456789 2.0 6 END In this case all other information about the Carbon atom (=6) is defaulted. Point charges cannot be inputted this way. 1.11111111 1.23456789 2.0 6 TABC1 if this is the case than there must be a $TABS section defining 'C1': $TABS C1 ZCORE = 4.00 NTYP = 3 NS = 2 ZETAS = 1.625 NP = 2 ZETAP = 1.595 # ND = 2 ZETAD = 1.595 IPD = -2.0 COULS = (in eV) COULP = (in eV) COULD = (in eZ) and COULF = (in eV) C2 .......... $END In the above all atoms with a tab of C1 will have the specified attributes: ZCORE is the core charge, and together with the atomic number = 0 in the $DATAIN section could specify a point charge. The value of ZCORE must be given if TABS are used <=====** NTYP as above. In this case a s,p,d basis set, with NS=NP=ND=2 A d polarization function has been added with exponent 1.595. An IP for the D orbital IPD has been added, as there is no default value for a 3d function on carbon. USS, UPP, UDD, UFF allows one to enter core integrals directly bypassing the use of the IPS, etc., in the calculation of USS,etc. These values are in Hartrees and are generally NEGATIVE. A # marks a continuation line follows for this tab. METHOD 3: Zmatrix input. If in the control block there is ENTYP = ZMAT -------- zmatrix input can be used. The format is identical to the one used in MOPAC and AMPAC, except that default connectivity for atoms 1, 2, and 3 is not supported. You will need to specify the full connectivity of all atoms. Example: $TITLEI Fe2-fdx -- Z-matrix model -- PDB-X-ray of Cyanobacteria Amobaena $END $CONTRL SCFTYP = ROHF RUNTYP = ENERGY NEL = 106 APX = INDO/1 INTTYP = 1 MULT = 11 UNITS = ANGS SCFTOL = 0.000001 ITMAX= 10 IPRINT = 0 ONAME = fe_zmat . . . ENTTYP= ZMAT $END $DATAIN X 0.000000 0 0.000000 0 0.000000 0 0 0 0 X 2.000000 0 0.000000 0 0.000000 0 1 0 0 Fe 1.350000 0 90.000000 0 0.000000 0 1 2 0 Fe 1.350000 0 90.000000 0 180.000000 0 1 2 3 S 2.190000 0 51.943492 0 90.000000 0 4 1 2 S 2.190000 0 51.943492 0 270.000000 0 4 1 2 S 2.290000 0 106.230000 0 90.000000 0 3 1 6 S 2.290000 0 106.230000 0 270.000000 0 3 1 6 S 2.290000 0 106.230000 0 90.000000 0 4 1 6 S 2.290000 0 106.230000 0 270.000000 0 4 1 6 C 1.820000 0 109.471220 1 180.000000 0 7 3 1 TABC1 . . . $END Again you may add the word TABXY, changing the defaults. For the above example there must be a C1 in a $TABS section. Atoms marked with X are dummy atoms, used for convenience if desired. For atom number 'a' : AT-SYMB R(AM) M1 THETA(AMN) M2 PHI(AMNO) M3 ATOM-M ATOM-N ATOM-O R(AM) is the distance between atom numbers A (this atom) and M, etc. in Angstroms unless UNITS = BOHRS in the $CONTRL section. M1, M2 M3 are for the moment ignored. If coordinates are to be frozen in a geometry optimisation thay must be frozen in the $INTCOR section. METHOD 4: PDB input: This is strictly formatted: Column: Content: 1 1-6 'ATOM' or 'HETATM' 2 7-11 Atom serial number (may have gaps) 3 13-16 Atom name in IUPAC standard format 4 17 Alternate location indicator(chain) A,B,C,etc. 5 18-20 Residue name in IUPAC standard format 6 22 RES LETTER 7 23-26 Residue sequence number (order as below) 8 27 LET2 9 28-30 Code for insertions of residues (ie 66A & 66B) 10 31-38 X coordinate 11 39-46 Y coordinate 12 47-54 Z coordinate 13 55-60 Occupancy 14 61-66 Temperature Factor 15 68-70 Footnote number SAMPLE INPUT 1----67---1b3--678-0b23--678-01------89------67------45----01----6b8-0 ATOM 15 SG CYS A 112 20.479 13.319 10.861 1.00 18.56 ATOM 16 1HB CYS A 112 19.270 11.709 9.494 1.00 0.00 ATOM 17 2HB CYS A 112 19.072 13.366 8.877 1.00 0.00 ATOM 37 CU CU A 130 -0.739 -0.425 3.680 1.00 0.00 NOTE THAT CHEMICAL SYBMOLS WILL BE RECOGNIZED. The above will be interpreted as Cu not a carbon atom on unit U -------------------------------------------------------------------- ---- Section II: Open shell (uhf) scf ------------------------------ -------------------------------------------------------------------- $TITLEI Water Positive Ion. An open-shell UHF calculation approximating the doublet state. 20 June, 1988. The title can be as long as you wish. $END $CONTRL SCFTYP = UHF RUNTYP = ENERGY ENTTYP = COORD UNITS = ANGS ASYM = C2V ! ***** Output file name ***** ONAME = waterp NEL = 7 MULT = 2 ITMAX = 20 SCFTOL = 0.000010 APX = INDO/1 INTTYP = 1 INTFA(1) = 1.000000 1.267000 0.585000 1.000000 1.000000 $END $DATAIN 0.000000 0.000000 0.000000 8 0.000000 1.000000 -1.000000 1 0.000000 -1.000000 -1.000000 1 $END ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: Input for OPEN SHELL UNRESTRICTED HARTREE FOCK SCF Explained ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: For open shell UHF calculations, the only changes in $CONTRL are: RUNTYP = UHF MULT = 2 NEL = 17 making the molecule open shell. No other changes are needed for UHF calculations. :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: Data for an OPEN SHELL RESTRICTED HARTREE FOCK SCF calculation :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: $TITLEI Make-believe open shell water doublet cation; an illustrative example. 5 July, 1988. $END $CONTRL SCFTYP = ROHF RUNTYP = ENERGY ENTTYP = COORD UNITS = ANGS ASYM = C2V NOP = 1 NDT = 1 FOP(1) = 6.0 1.0 ! ***** Output file name ***** ONAME = water NEL = 7 MULT = 2 ITMAX = 20 SCFTOL = 0.000010 INTTYP = 1 APX = INDO/1 INTFA(1) = 1.000000 1.267000 0.585000 1.000000 1.000000 $END $DATAIN 0.000000 0.000000 0.000000 8 0.000000 1.000000 -1.000000 1 0.000000 -1.000000 -1.000000 1 $END ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: Input for OPEN SHELL RESTRICTED HARTREE FOCK SCF Explained ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: For open shell RHF calculations additional data is required SCFTYP = ROHF MULT = 2 NEL = 7 NOP = 1 ----- The number of open shell orbitals NDT = 1 ----- The class of the open shell state see below for classes available FOP(1) = 6.0 1.0 ----- The number of electrons in each shell First number is number of electrons in closed shell. For default cases, second number is total number of electrons in all open shells. Default cases: Let FF = Number of closed shell electrons A) One electron, one open orbital --- DOUBLET NOP = 1 NDT = 1 FOP(1) = FF.000000 1.000000 B) N electrons, N open orbitals --- Highest spin case (ie 4 electrons, 4 open orbitals --- QUINTET) NOP = 4 NDT = 1 FOP(1) = FF.000000 4.000000 C) One electron, N open orbitals (ie N=4 --- DOUBLET) NOP = 4 NDT = 1 FOP(1) = FF.000000 1.000000 D) Two orbitals, one electron --- DOUBLET See C Two orbitals, two electrons --- TRIPLET See B Two orbitals, two electrons --- SINGLET Two types One electron in each orbital NOP = 2 NDT = 1 FOP(1) = FF.000000 2.000000 Two electrons in one orbital, none in the other XaXb+YaYb NOP = 2 NDT = 2 FOP(1) = FF.000000 2.000000 Two electrons in one orbital, none in the other XaXb-YaYb NOP = 2 NDT = 3 FOP(1) = FF.000000 2.000000 XaXb+YaYb and XaXb-YaYb are degenerate in certain groups E) Three electrons, two open orbitals --- DOUBLET NOP = 2 NDT = 1 FOP(1) = FF.000000 3.000000 F) Averaged multiplet, M open orbitals with N electrons This is the CAHF option. NOP = M NDT = 9 FOP(1) = FF.000000 N From orbitals obtained from the Configuration Averaged Hartree Fock calculations, a Rumer CI (see below) can be performed to project out states of a specific multiplicity or symmetry. In such a case it is best to store the vectors (VEC=9) and restart the CAHF calculation and Rumer CI after examining the nature of the orbitals obtained. Open shell RHF -- General case Requires input of vector coupling coefficients MIM(2) = 3 2 ----- Total number of orbitals per open shell AR(1) = 1.0 -1.0 0.0 ----- The alpha vector coupling coefficients read in as a linearized matrix NOTE alpha = 1 - A A is from the energy expression BR(1) = -1.0 -1.0 2.0 ----- The beta vector coupling matrix NOTE beta = 1 - B B is from the energy expression. EXAMPLE --- 3 degenerate orbitals, 4 electrons, TRIPLET NOP = 3 NDT = 0 FOP(1) = FF.000000 4.000000 MIM(2) = 3 0 AR(1) = 0.062500 BR(1) = -0.125000 -------------------------------------------------------------------- ---- Section III: Configuration interaction ------------------------ -------------------------------------------------------------------- $TITLEI HC=C-CN For G. Diercksen Max Planck Institute for Astrophysics $END $CONTRL SCFTYP = RHF RUNTYP = CI ENTTYP = COORD UNITS = ANGS ASYM = C2V INTTYP = 1 APX = INDO/1 NEL = 18 MULT = 1 ITMAX = 20 INTFA(1) = 1.000000 1.267000 0.585000 1.000000 1.000000 ! ***** C.I. size information ***** CISIZE=100 ACTSPC=17 ! ***** Output file name ***** ONAME = HCCCN $END $DATAIN 0.000000 0.000000 2.568000 7 0.000000 0.000000 1.378000 6 0.000000 0.000000 0.000000 6 0.000000 0.000000 -1.205000 6 0.000000 0.000000 -2.263000 1 $END $CIINPU 2 1 10 1 0 0 0 1 1 2 10 -60000.00 0.000000 0 0 0 0 0 0 0 0 0 1 9 9 21 1 9 10 17 $END :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: Input for CONFIGURATION INTERACTION Explained :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: Changes to the $CONTRL section consist of the following: RUNTYP = CI CISIZE=101 ACTSPC=17 CISIZE = 101 -- The CI is expected to generate no more than 100 configurations in EACH irrep of the group (C2V) plus the generating state ACTSPC = 17 -- The last active orbital in this CI is the (virtual) orbital 17 For special CI use value of (MOMAX-MOMIN+1) For general CI use value of (MOMAX) For MP/2 use value of (MOMAX) Some old data sets may contain an array DYNAL. The 6-th element of DYNAL is the same as CISIZE, and the 7-th element is ACTSPC. Other elements are ignored. An additional section, $CIINPU has been added which details the type of configuration interaction calculation to be done Briefly, the CI input consists of: (A) Initial CI switches (FORMAT 11I5) (B) Thresholds for reducing the number of configurations (2F10.6) (C) Point group and irrep specification (9I5) (D) Symmetry information (OMIT if symmetry is used in SCF) (40I2) (E) Orbital occupancy of reference determinant(s) (16I5) (F) Excitation information (16I5) *** NOTE *** THIS IS FORMATTED INPUT!!! (A) Initial CI switches; eleven switches in 11I5 FORMAT This is known below as the "CI LINE" N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11 N1 = 1 ----- Calculate only the diagonal elements of CI matrix = 2 ----- CI for SINGLETS from closed shell reference or SIngles only for a ground state doublet = 3 ----- CI for TRIPLETS from closed shell reference = 4 ----- CI for TRIPLETS and SINGLETS or SIngles only for a ground state doublet for the DOUBLETS and QUARTETS = 5 ----- General CI using Rumer diagrams, any multiplicity Use for ROHF SCF ground states = 9 ----- GUGA CI. This generates input for the DRT program, then TRN program then SDG program, see appropriate help files. =20 ----- MP/2 perturbation theory =21 ----- Nesbet-Epstein second order perturbation theory =50 ----- Double Group CI (with Spin-Orbit) N2 = 1 ----- The number of reference determinants to be used to generate the excited configurations. If this is an MP/2 calculation on a UHF wavefunctio then N2 = 2, one for alpha and one for beta orbital Only for Rumer diagram CI (N1 = 5) can there be more than ONE reference determinant. N3 = 0 ----- The number of roots of the CI matrix to calculate DEFAULT is the 10 lowest N4 = 1 ----- The multiplicity of the CI. It need not be the the same as that of the reference SCF Natural Orbital Section--Available only for Rumer CI (N1 = 5) N5 = N ----- Perform Natural Orbital Optimization on state N DEFAULT = 1. This option works only if N1 = 5 N6 = M ----- Average the first M densities for NO'S DEFAULT=1. N7 = 0 ----- Do not perform natural orbital optimization = 1 ----- Perform non-iterative NO analysis = N ----- Perform N iterations in the NO analysis This option works only for the Rumer diagram CI Transition Moment Section N8 = 0 ----- Do not calculate transition moments > 0 ----- Calculate the transition moments between N9 = states N8 through N9 into N10 through N11 N10 = DEFAULT is N9 = 1 N10 = 2 N11 = 10 N11 = (B) Criteria to reduce the number of configurations included in the CI ECUT COMP (FORMAT 2F10.6) ECUT = 0 or a negative number for normal calculation = Positive threshold value (in cm-1) below which all configurations are included. For example a value of 60000. means any configuration with a DIAGONAL CI element less than 60,000 cm-1 is included COMP = A value indicating the extent of interaction to be included For example a value of 500.0 (cm-1) means that ANY generated configuration having an OFF DIAGONAL CI element larger than 500 cm-1 with any of the states accepted by ECUT (above) is included. A value of 0.0 includes all configurations (C) Point group symmetry information (FORMAT 9I5) ISYM IREP IREP IREP IREP IREP IREP IREP IREP ISYM = N ----- the order of the Abelian group followed by UP TO eight IREPPs to be considered, in turn, for the CI. IF NO SYMMETRY IS TO BE CONSIDERED LEAVE THIS LINE BLANK. or ISYM = 0. If symmetry is assigned, eg., ASYM = C2V, or DETSYM = 1, and the program determines symmetry, and if all the CI's for the different irreducible representations are the same, then a single master codetor and generating line can be used if you do not specify a different master codetor and generating line. This also works if DETSYM = 1 and ISYM = -1 EXAMPLES: 4 1 2 3 4 ----- do all four irreps for C2V 2 2 1 ----- do irreps 2 and then 1 for C2 8 6 7 8 ----- do the last 3 irreps for D2H Character tables for Abelian groups ISYM=2: IRREP CI C2 CS 1 1 1 Ag A A' 2 1 1 Au B A'' ISYM=4 IRREP C2H C2V V=D2 1 1 1 1 1 Ag A1(Z) A1 2 1 1 -1 -1 Au(Z) A2 B1(Z) 3 1 -1 1 -1 Bu(X/Y) B1(X) B2(Y) 4 1 -1 -1 1 Bg B2(Y) B3(X) ISYM=8 IRREP D2H 1 1 1 1 1 1 1 1 1 Ag 2 1 1 1 1 -1 -1 -1 -1 Au 3 1 1 -1 -1 1 1 -1 -1 B1g(XY) 4 1 1 -1 -1 -1 -1 1 1 B1u(Z) 5 1 -1 1 -1 1 -1 1 -1 B2g(XZ) 6 1 -1 1 -1 -1 1 -1 1 B2u(Y) 7 1 -1 -1 1 -1 1 1 -1 B3u(X) 8 1 -1 -1 1 1 -1 -1 1 B3g(YZ) (D) Orbital symmetry specifications >>>>> USUALLY OMITTED <<<<< CI Specification(s) *** NOTE: *** If the CI is done on more than one irrep, then the CI specification lines must be repeated for each irrep considered THERE MUST BE A REFERENCE DETERMINANT AND GENERATING LINES FOR EACH IRREP CONSIDERED. (E) First line ----- The number of generating lines and the reference determinant in FORMAT nI5 EXAMPLE: 2 4 4 5 Means there are two lines specifying excitations from the reference determinant: (1a,1b,2a,2b,...4a,4b,5a) The list must start with a closed shell alpha/beta pair followed by open shell coupled alpha/beta pairs and ending with unpaired alpha orbitals. For closed shell cases specify only the outermost occupied pair For ordinary CI (N1 = 2) only one reference determinant is allowed. For Rumer CI (N1 = 5) several reference determinants are allowed and these do NOT need to be the SCF determinant. In addition, for many open shells it is convenient to use the words DOC(doubly occuppied), SOC (singly occuppied) and VIR (virtual or empty). For example, 2 4 4 5 ----> 2 4*DOC SOC 1 3 3 5 5 4 ----> 1 3*DOC SOC DOC 1 3 3 5 5 ----> 1 3*DOC VIR 1*DOC NOTE: REFERENCE DETERMINANT(S) AND GENERATING LINES ARE REQUIRED FOR EACH IRREP CALCULATED (F) Second line(s) ----- Generating lines in FORMAT 16I5 COLUMNS 1-5 = 1 Individually specified singly excited configurations = 2 Individually specified doubly excited configurations = 21 Multiply specified singly excited configurations = 22 Multiply specified doubly excited configurations = 32 Multiply specified TYPE I doubly excited configurations COLUMNS 6-78 = Occupied orbitals --> Virtual orbitals Examples of CI specification lines 1 4 5 ----- One singly excited configuration with electron removed from MO 4 and placed into MO 5 (4 INTO 5) or 21 2 4 5 6 ----- All possible singly excited configurations generated by removing electrons from MO 2 through 4 and placing them into MO 5 to 6, one electron at a time. (2-4 INTO 5-6) or This is equivalent to specifying the following 1 2 5 1 3 5 1 4 5 1 2 6 1 3 6 1 4 6 2 2 5 4 8 ----- One doubly excited configuration (2 INTO 5, 4 INTO 8) 2 I A J B ----- I into A, J into B, requires that I .LE. J and A .LE. B 22 2 4 5 8 1 3 5 8 ----- Multiply specified double excitations (2-4 into 5-8 and 1-3 into 5-8) *** NOTE *** All ' 2X' lines (multi-configurations) before ' X' lines (single configurations) ALL INDIVIDUALLY SPECIFIED CONFIGS AND REFERENCE DETERMINANTS ARE INCLUDED, REGARDLESS OF SYMMETRY! TRIPLES AND QUANDRUPLES BEFORE SINGLES AND DOUBLES SPECIFIED FULL CI AFTER ALL OTHERS. ie 23 2 5 6 9 21 1 5 6 10 22 1 5 6 10 1 5 6 10 29 4 5 6 7 *** If N1 = 5 (Rumer CI) Additional generating lines are allowed 21.... SINGLES. 22.... DOUBLES 23.... TRIPLES 24.... QUADS 29 3 5 6 10 FULL CI between orbitals 3-5 into 6-10 For the Rumer CI, the multiplicity of the CI may be different from the multiplicity of the reference determinant. Under those circumstances, the reference determinant used for generating the list of configurations may not, itself, be included in the list of configurations *** If N1 = 20 (MP/2) Only one reference determinant is allowed. In the case of UHF, specify BETA symmetry, reference determinant, and ONLY ONE GENERATING LINE. Then repeat for ALPHA set. EXAMPLE: (blank line) ----- (No cutoff or threshold) 4 1 ----- (4 irreps, do only irrep No. 1) 1 2 4 3 1 2 3 1 ----- (Sym of BETA MO.'s) 1 1 2 3 4 ----- (One Gen line, 1-2-3-4 are BETA) 22 1 4 5 8 1 4 5 8 ----- (Multiple doubles, 1-4 into 5-8) (now repeat for alpha spin) 1 2 4 3 1 3 2 1 ----- (ALPHA and BETA sym not the same) 1 1 2 3 4 5 ----- (ALPHA occupied in aufbau order) 22 1 5 6 8 1 5 6 8 ----- (Note extra alpha electron) ---ADDITIONAL CONFIGURATION INTERACTION SPECIFICATIONS--- 21 2 4 5 8 3 4 ---- All excitations (2-4 TO 5-8) but only those with MOs (2-4) with large AO character of type 03 (PY) and with MOs (5-8) with large AO character of type 04 (PZ) This option does not work for singly specified configurations (0001, etc) 1=S, 2=PX, 3=PY, 4=PZ, 5=D(Z2), 6=D(X2-Y2), 7=D(XY), 8=D(XZ), 9=D(YZ). or 22 2 4 5 8 1 3 5 8 4 4 ----- All doubly excited configurations (2-4 TO 5-8, 1-3 TO 5-8) but only when MOs 2-4 and 1-3 have SMALL type 04 contributions and MOs 5-8 and 5-8 have SMALL 04 contribs. or 32 1 5 6 9 ----- Singlet configurations, all possible double excitations removing 2 electrons from MO 1 and placing both in MO 6. Then 2 electrons from 1 into 7,... 2 electrons from MO 5 into MO 9 (Type I doubles 1-5 into 6-9) 42 1 6 2 8 3 7 4 10 11 12 ----- Double excitations 1 into 6 with 2 into 8 and 1 into 7 with 2 into 10 and 1 into 11 with 2 into 12 and 3 into 6 with 4 into 8 and 3 into 7 with 4 into 10 and 3 into 11 with 4 into 12 $END There is also a I4,20I2 format supported for input, but it is provided for backward compatibility only and it should not be used in new input files. The program will automatically choose the correct format. The use of symmetry in the CI will generate a Summary table at the end which eleminates reduntant states, and orders the states in increasing energy. Reduntant states are those that are specified singly, or those that are used to generate other states (The Master Codetor's). The really belong only to their own irreps, but serve as markers for the calculation. On occasion the CI will change the lowest energy state to be other than that used as the marker in each irrep. If this should happen, then the oscillator strength will not be printed for that irrep in the summary table, as it will have been calculated from the lowest configuration in each irrep, and not neccesarily from the lowest energy (ground) state of the molecule. To correct this situation, the lowest energy state of the molecule should be specified in each irrep singly, so this state is the lowest energy in each irrep. ***AUTOMATIC CI There is an automatic option for generating closed shell CI This will generate a 10 up 10 down CI. $CIINPU N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11 as before EPS ECUT as before 0 = ISYM or -1 see below -1 generate the 10 up 10 down $END If ISYM = -1 above, and DETSYM = 1 in the $CONTRL block, the CI will automatically be symmetry blocked. If N10 is a number less than N9 then the excited state spectrum between states will also result. For example, if N8 = 1, N9 = 10, N10 = 1 and N11 = 50, all states from 1 thru 10 into 1 thru 50 will be calculated. In addition each of the first 10 states will be analyzed and the population analysis printed (in the ZDO basis). If bond orders are desired for each of the states N10 through N9, then CIBONDS should appear as a keyword in the $OUTPUT section. *** -------------------------------------------------------------------- ---- Section IV: Geometry optimization ----------------------------- -------------------------------------------------------------------- $TITLEI NH3 BFGS UPDATE, April 6, 1988 $END $CONTRL SCFTYP = RHF ENTTYP = COORD UNITS = ANGS RUNTYP = GEOM INTTYP = 0 APX = INDO/1 III = 2001 NEL = 8 MULT = 1 ITMAX = 12 SCFTOL = 0.000000 ! ***** Interaction factors ***** INTFA(1) = 1.0 1.0 1.0 1.0 1.0 1.0 ! ***** Output file name ***** ONAME = g1 $END $DATAIN 0.000000 0.000000 0.000000 7 1.026604 0.000000 -0.411484 1 -0.513302 0.889066 -0.411484 1 -0.513302 -0.889066 -0.411484 1 $END ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: Input for GEOMETRY OPTIMIZATION Explained ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: The following switches should be set to run a geometry optimisation RUNTYP = GEOM ----- Geometry Optimization INTTYP = 0 ----- Theoretical Gammas <<<<< MOST IMPORTANT SCFTOL = 0.00 ----- SCF states must be well converged INTFA(1) = 1.0 1.0 1.0 1.0 1.0 1.0 In addition, a number of switches may be set in order to control the details of the geometry optimization procedure. The most important switch for geometry optimisation is III which is a four digit integer made up of 4 parts: IA:IB:IC:ID Choose a value for each of IA, IB, IC, ID and concatenate to form a 4 digit integer from these values. Enter this value for III. For normal calculations the following switches are recommended. III = 0000 ----- NO GEOMETRY OPTIMISATION = 2000 ----- for ground state structures = 3120 ----- for transition state calculations Additional possibilities (for experienced users) are: -- Search for minimum, transition state, etc.? IA = 0 energy calculation only (No optimization) = 1 energy and gradient calculated (No optimization) = 2 for stable geometry = 3 for transition state = 4 for transition state restart (not operational) -- Type of Optimisation -- IB = 0 Newton Raphson = 1 Augmented hessian if transition state followed by f+f = 2 Minimize norm squared of gradient (full treatment) = 3 Homotopic path continuation (with IB = 2) = 4 Mimimize norm squared of gradient (approx. treatment) = 5 Homotopic path continuation (with IB = 4) (** = 6 Gradient extremal for transition states. For example III = 3620. Note you must include a target set of coordinates even though they are not used as is needed for all transition set calculations.**) = 7 LTP option for transition states. (** = 8 use Newton-Raphson with trust radius to control step length after either Augmented hessian or gradient extremal have found 1 negative root of the hessian.( see note below regarding use of IP and IQ ) **) -- Type of search -- IC = 0 Updated Hessian = 1 Updated Hessian with last iteration with analytic Hessian = 2 Analytic Hessian = 3 gradient only, no Hessian = 4 Analytic Hessian calculated with first order approximation = 5 Analytic Hessian calculated with second order approximation -- Threshold for convergence -- ID = 0 Optimisation converged when component of grads < 1.D-3 = 1 converged when component of grads < 5.D-4 = 2 converged when component of grads < 1.D-4 = 3 converged when component of grads < 1.D-5 = 4 converged when component of grads < 1.D-6 = 5 converged when step components < 1.D-4 = 6 converged when energy change < 5.D-7 = 7 converged when grad norm < 1.D-3 = 8 converged when grad norm < 5.D-4 = 9 converged when grad norm < 1.D-4 (** NOTE: For special transition state calculations III can be used as a six digit integer of the form IP:IQ:IA:IB:IC:ID. Here IP and IQ can be used to override the default options built in for the Augmented hessian and gradient extremal methods, viz. Allowing the use of Newton-Raphson with step length controlled by a trust region to move to the nearest extreme point, after the hessian attains 1 negative eigenvalue (IP=8). This option is useful to override the default minimization of norm squared of the gradient when using Augmented hessian. This feature may also be useful when using gradient extremal. IP can take values 4 and 8 corresponding to the values of IB and IQ can take values 2, 4 and 5 corresponding to values of IC. If the V1 approximation to the exact analytic hessian is chosen (IB=4), then care must be exercised in the choice of a mode since the eigenvalues of the V1 hessian may be depressed in comparison with those of the exact analytic hessian. A good choice of MODE in such cases is 3. **) ** Other Geometry Switches ** MODE refers to the initial vibrational mode to be followed by the transition state search in a "break-up" or rearrangement reaction. ITYPE controls the type of update procedure used ITYPE = 1 <<<<< BFGS UPDATE (DEFAULT) = 2 ----- MURTAGH-SARGEANT (OLD FNMIN) = 3 ----- DFP = 4 ----- GREENSTADT LMASS = .TRUE. <<<<< if mass scaled coordinates are used = .FALSE. ----- if not RHO = 0.03 <<<<< DEFAULT 0.50 ----- an exact line search, DON'T DO IT! ----- 0.01 < RHO < 0.45 is a typical range SIGMA = 0.9 <<<<< DEFAULT (a loose line search) = 1.0 ----- any decrease in energy = 0.5 ----- exact line search, DON'T DO IT! ----- 0.55 < SIGMA < 0.95 is a typical range PHASE is a parameter used for transition state calculations PHASE < -4.5 ----- Energy is maximized along the direction vector between reactants and products or guessed transition state PHASE < -3.5 ----- First move is along mode of Hessian that most strongly overlaps with the vector between reactants and products or guessed transition state PHASE < -2.5 ----- First move is along mode of Hessian that most strongly overlaps with input direction vector PHASE < -1.5 ----- phase of move along chosen mode is determined by the vector between reactants and products or guessed transition state (For stable state calculations, phase of move along chosen mode is determined by the vector between transition state and reactants) PHASE = -1 ----- phase of chosen mode of Hessian is reversed PHASE = +1 ----- phase of chosen mode of Hessian is unchanged LINV = .TRUE. ----- Inverse Hessian is used = .FALSE. ----- Direct Hessian is used (This depends on ITYPE) If one wants an Updated Augmented Hessian then LINV must be set FALSE on input. LEXACT = .TRUE. ----- Once negative eigenvalue is found in a transition state calculation with subroutine SADDLE, then exact method for minimizing the norm of the gradient is used ISRCH = 1 ----- Normal line search method (subroutine SEARCH) = 2 ----- Alternate method (subroutine STPSIZ) STPTOL = 0.4 au ----- Maximum allowed stepsize norm (for IC = 4) DEFAULT = 0.4 au ** NOTE ** The program will accept internal coordinates and constrained optimisation is allowed in internal coordinates. Specification of internal coordinates are described below and are completely general. The internal (or valence bond) coordinate option is an alternative to the more conventional approach of minimizing molecular energies with respect to cartesian coordinates. Internal coordinates form a natural approach to constrained optimization problems. In a large molecule or cluster one may be interested in optimizing a limited number of bond lengths and/or bond angles. Experience, however, has indicated that the initial complete optimization of large systems may be better performed using the cartesian coordinates approach. The cartesian approach usually does not produce large relative atom movements, whereas the internal procedure links together atom movements and can result in large displacements, particularly of the end atom in a long chain of atoms. Basic outline of the internal coordinate procedure: As in any standard molecular calculation a set of cartesian coordinates is read in by the program, the atom labels correspond to the order in which the atomic coordinates are read in (i.e., atom 1 corresponds to the first line of coordinates, 2 the second line etc.). Then a separate set of internal coordinates, which are specilfied by the relevant atom labels, are read in from the group $INTCOR ! An example of some internal coordinates for water. INTERNALS 102 103 20103 $END The different internal coordinates are: - a) Bond Lengths - designated by two integer atom labels i and j b) Bond angles - denoted by three atom labels i, j, k where j is the atom at the vertex of the angle. c) Torsion and wag angles - these require 4 atom labels i, j, k, l as well as an integer indicating the appropriate coordinate type. ITYPE = 1 : ijkl - the torsional coordinate is the angle between the planes ijk and ijl. l / j--i \ k ITYPE = 2 : ijkl - this type is similar to type 1 however atom l is joined to atom j. Again the coordinate is the angle between the planes ijk and ijl. l / i--j / k ITYPE = 3 : ijkl - this is a wag coordinate, atoms ijk define a plane and the angle gives the line il out of the plane ijk. \ l j t \ / ---- i \ k ITYPE = 4 : ijkl - same as 3 but the angle is 180-(angle from 3). j | l | / |/ t i ----l \ \ k Input of Internal coordinates: Each input line with internl coordinate data specifies the position of one new atom relative to atoms with known positions. Line 1: A bond length coordinate. This gives the labels for the initial two atoms from which the complete system is built up. Line 2: Bond length coordinate and either an angle coordinate or another bond length. These two coordinates relate the third atom to the first two. Remaining lines: Each remaining atom is specified in turn by three internal coordinates. Each of these coordinates should only include one atom label not previously specified. The various combinations of allowed coordinates are: - 1) Three bond lengths ril, rjl, rkl ; positions atom l 2) One bond length ril and two bond angles Ojil, Okil. 3) One bond length, one bond angle, and one torsion angle. Common combinations are a) ril, Ojil, tijkl (ITYPE=1) b) rjl, Oijl, tijkl (ITYPE=2) c) ril, Ojil (or Okil), tijkl (ITYPE=3 or 4) 4) Two bond lengths and one torsion angle. These coordinates enable the closure of rings of atoms, e.g. in the figure, l is the only previously unspecified atom. Ring closure can be effected by: - ----h \ l / i----j / \ k k' a) rjl, rhl, tijkl (ITYPE=2) b) rjl, rhl, tjik'l (ITYPE=1) A total of (N-1) data lines are required for input, where N is the number of atoms in the system. Each coordinate is expressed as a single integer using the rule: - a) Bond length rij = I*100 + J: i.e., 102 for r12 b) Bond angle Oijk = I*1000 + J*100 + K c) Torsion tijkl = I*10000000 + J*100000 + K*1000 + L*10 + ITYPE Constrained Optimization A coordinate is not optimized when it is input as a negative integer, i.e., -010203 fixes angle O123. The program allows scale factors to be associated with each coordinate. However, when no scale factor is given the default is one. Data Format: Line 1: bond length (and scale factor) I5,F10.6 Line 2: 2nd and 3rd coords. (and factors) I5,I7,2F10.6 . Line N-1: 3 coords (and factors) I5,I7,I10,3F10.6 NOTE Bond lengths are listed before bond angles, which in turn are listed before torsion angles on each line. Error checks and redundant coordinates. The subroutines in the internal coordinate package make several simple checks for errors in the input coordinates and prints out self-explanatory error messages. A more difficult error is associated with redundant coordinates. For example consider NH3: H | Ob | Oa N / \ /Oc \ H H The figure above indicates a suitable set of coordinates when the molecule is non-planar. However if NH3 becomes planar then one of the bond angles is redundant since Oa + Ob + Oc = 360 and there is no coordinate present describibg the atomic coordinates perpendicular to the plane of the molecule. An error in the program occurs because the redundant coordinates produce a singular coordinate transformation matrix which needs to be inverted. To diagnose the redundant coordinate the transformation matrix is diagonalized, and the eigenvector (or vectors) associated with zero eigenvalue groups together with the redundant coordinates. If a coordinate is entered twice, one of the coordinates will be found as a redundant coordinate. Constrained optimisation can also be done in cartesian coordinates. This also requires an INTCOR Block. $INTCOR ! An example of a four atom system in which the second and third atoms ! have there z coordinates frozen during the geometry optimisation. CARTESIANS 1.000000 1.000000 1.000000 <-- this is the x, y and z scaling 1.000000 1.000000 0.000000 factors of atom 1 in free format 1.000000 1.000000 0.000000 1.0=full optimisation 1.000000 1.000000 1.000000 0.0=completely frozen $END -------------------------------------------------------------------- ----- Section V: Electron assignment ------------------------------ -------------------------------------------------------------------- $TITLEI Hexamino-cobalt(II) - quartet C.I. from doublet ROHF - assign electrons April 6, 1988 $END $CONTRL SCFTYP = ROHF RUNTYP = CI ENTTYP = COORD UNITS = ANGS ASYM = CS INTTYP = 1 APX = INDO/1 NEL = 55 MULT = 2 ITMAX = 10 SCFTOL = 0.000110 ! ***** C.I. size information ***** CISIZE=200 ACTSPC=45 ! ***** ROHF information ***** NOP = 2 NDT = 1 FOP(1) = 54.000000 1.000000 ! ***** Interaction factors ***** INTFA(1) = 1.00000 1.26700 0.64000 1.00000 1.00000 1.00000 ! ***** Output file name ***** ONAME = ci1 $END $DATAIN 0.000000 0.000000 0.000000 27 0.000000 0.000000 2.200000 7 0.000000 -0.980520 2.546670 1 -0.849160 0.490260 2.546670 1 0.849160 0.490260 2.546670 1 0.000000 0.000000 -2.200000 7 0.000000 -0.980520 -2.546670 1 0.849160 0.490260 -2.546670 1 -0.849160 0.490260 -2.546670 1 2.200000 0.000000 0.000000 7 2.546670 -0.980520 0.000000 1 2.546670 0.490260 0.849160 1 2.546670 0.490260 -0.849160 1 -2.200000 0.000000 0.000000 7 -2.546670 -0.980520 0.000000 1 -2.546670 0.490260 -0.849160 1 -2.546670 0.490260 0.849160 1 0.000000 -2.200000 0.000000 7 0.980520 -2.546670 0.000000 1 -0.490260 -2.546670 -0.849160 1 -0.490260 -2.546670 0.849160 1 0.000000 2.200000 0.000000 7 -0.980520 2.546670 0.000000 1 0.490260 2.546670 -0.849160 1 0.490260 2.546670 0.849160 1 $END $CIINPU ! ***** Configuration Interaction specification ***** 5 3 10 4 0 0 0 0 0 0 0 -60000.0 0.000000 2 1 2 2 26 26 27 27 28 21 20 28 28 34 22 23 28 28 29 23 28 28 29 2 26 26 27 27 29 21 20 29 28 34 22 23 29 28 29 23 29 28 29 2 25 25 28 28 29 29 26 21 25 29 26 27 22 25 29 26 27 25 29 26 27 2 26 26 27 27 28 21 20 28 28 34 22 23 28 28 29 23 28 28 29 2 26 26 27 27 29 21 20 29 28 34 22 23 29 28 29 23 29 28 29 2 25 25 28 28 29 29 26 21 25 29 26 27 22 25 29 26 27 25 29 26 27 $END $ASSINP ! ***** Electron assignment specification ***** 10 7 5 5 0 0 0 0 0.000000 5 0.400000 0 0.000000 0 0.000000 0.000000 6 0.400000 0 0.000000 0 0.000000 2.000000 7 0.400000 0 0.000000 0 0.000000 2.000000 8 0.400000 0 0.000000 0 0.000000 2.000000 9 0.400000 0 0.000000 0 0.000000 0.500000 5 0.400000 0 0.000000 0 0.000000 0.500000 6 0.400000 0 0.000000 0 0.000000 0.000000 7 0.400000 0 0.000000 0 0.000000 0.000000 8 0.400000 0 0.000000 0 0.000000 0.000000 9 0.400000 0 0.000000 0 0.000000 $END ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: Data for ELECTRON ASSIGNMENT explained ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: $ASSINP Switches for assignment of electrons to MOs are in FORMAT 8I5 Several options exist for assigning orbital occupations and are determined by the value of NASS(1) NASS(1) = 0 <<<<< Molecular orbitals are filled in order of increasing orbital energy (aufbau) NASS(1) =-1 ----- For ROHF calculations: MOs are rearranged and the lowest NEL/2 are filled. NASS(1) =-2 ----- Molecular orbitals are filled on the basis of symmetry information NASS(1) > 0 ----- Orbital occupations are assigned on the basis of the atomic orbital character of the MOs. --- For NASS(1) > 0 --- First Line FORMAT 8I5 NASS(1) = J ----- J is a positive number specifying the the number of lines of data to be read in NASS(2) = K ----- K is the total number of ELECTRONS to be assigned by this method NASS(3) = 0 ----- For closed shell RHF = L ----- Assign L ALPHA orbital occupancies (UHF) Assign L CLOSED shell orbitals (ROHF) NASS(4) = M ----- Assign M BETA orbital occupancies (UHF) Assign M orbitals to the first open shell (ROHF) NASS(5) = N ----- Assign N orbital occupations in subsequent NASS(6) open shell(s) (ROHF). NASS(7) NASS(8) --- For NASS(1) > 0 --- Subsequent line(s) Orbital occupancies (by shells) as listed above. FORMAT for specifying occupancy is given by the values of ELECTRONS AO-SPECS THRESHOLD (F10.6,3(I5,F10.6)) ELECTRONS ----- The number of electrons to be assigned to a particular MO. This is a FLOATING POINT number ranging from 0.0 (a hole) to 2.0 (F10.6) AO-SPECS ----- The number of the AO basis function as it appears in the MO. AO 3 would be the third basis function. AO-SPEC is an I5 integer that may specify up to two different AOs. A value of 05025 specifies both AO 5 and AO 25. (I5) THRESHOLD ----- The test used to determine the character of the MO As many as three pair of (AO/THRESH) can be specified on each line. (F10.6) EXAMPLES: 10 7 5 5 ----- There are 10 lines assigning 7 electrons, 5 for the first shell, and 5 for the second 0.000000 5 0.4 ----- Assign ZERO electrons to the MO which has a coefficient for AO number 5 that when SQUARED is larger than 0.4 Nine more lines are required for this example 3 2 0 2 1 ----- 3 lines assigning TWO electrons, none for the closed shell, two for the first open shell, one for the second. 0.00000 3 5 -0.200000 ----- Assign zero electrons to the MO in which the product of the coefficients for AO 3 and AO 5 is a larger negative number than -0.2000000 This line is for the first open shell 1.00000 22 -1.00000 ----- Assign two electrons to the MO with a node on AO 22 for second open shell 2.00000 20 0.400000 25 0.400000 ----- Assign two electrons to the MO with coefficients for AO 20 > 0.4 and for for AO 25 > 0.4 ** NOTE ** MOs are scanned from the HOMO/LUMO gap going up 1, then going down 1, then up 2, down 2,... until all assignments are satisfied. --- NASS(1) = -1 --- Next line specifies rearranged order of starting vectors in (16I5). First orbital and last orbital specified must not be rearranged. Note that this requires the use of starting vectors and the rearrangment only takes place on the first cycle. Subsequent cycles revert to NASS(1) = 0 BECAUSE OF ORBITAL RELAXATION, THIS IS A DANGEROUS OPTION! For UHF, two such lines must be given, first for beta spin orbitals, then alpha. EXAMPLE(RHF): -1 3 4 5 7 6 8 ----- Specifies transposing MO 6 and MO 7 before filling by aufbau. This procedure is only done on the first cycle. All other cycles are done by aufbau. --- For NASS(1) = -2 --- NASS(2) = 0 NASS(3-7) = 0 or 1. A zero specifies that the orbitals of this operator are to be filled by the aufbau principal, a one specifies that this shell will be symmetry assigned by the following lines. For this case the number of mo's in each symmetry type are given in order. The format is 8I5. i.e: -2 9 0 1 1 1 0 ---NASS. 4 3 2 1 ---second shell 0 1 1 1 ---third shell 0 0 1 2 ---fourth shell This is an example of an open shell ROHF calculation with five shells. The first shell is filled by aufbau, the second shell has 4 mo's of irrep 1, 3 of irrep 2, 2 of irrep 3, and 1 of irrep 4. The next open shell has no mo's of irrep 1 filled, 1 of irrep 2, one of irrep 3, and one of irrep 4. -------------------------------------------------------------------- ---- Section VI: Calculation of Polarizabilities ------------------ -------------------------------------------------------------------- IN the $CONTRL block add RUNTYP = CI POLAR = 1 <--- This is Bill PArkinson's TDA and RPA for alpha, TDA for beta and gamma. and approx. RPA for beta. This is fast for alpha and beta, and the size of the CI should be set equal to the particle*hole space + 1 in DYNAL (sixth entry) CAUTION: THE CI LINE DETERMINES THE HOLE AND PARTICLE SPACE INCLUDED IN THE CALCULATION SEE THE GENERATING LINE = 2 <--- This is Kanis for frequency dependent beta. CAUTION: THE NUMBER OF STATES INCLUDED WILL NOT EXCEED N3 ON THE CI LINE. A selection of states based on the energy differences between ground and excited states is made. If these states do not contain the oscillator strength, the results will not be good. This code has undergone major restructuring, and it is unlikely problems here are the fault of Dave Kanis! = 3 <--- This is both of the above = 0 <--- This is the default: do not calculate pol- arizabilities. If using the frequency dependent Kanis code, these frequencies can be specified in the $CONTRL block. $CONTRL . . FREQ(1) = 0.000 0.650 1.12 1.30 <-- up to 6 in ev. FREQ(1) = 0.000 0.000 <-- only static polarizabilities. FREQ(1) = 0.000 2.000 -1.000 <-- six frequencies will be calculated from 0.0ev to 2.00ev in equal steps. If no frequencies are given, the 3 defaults are 0.0, 0.6491 and 1.17 ev -------------------------------------------------------------------- ---- Section VII: Spin-orbit calculations--------------------------- -------------------------------------------------------------------- $TITLEI Cerium Oxide Double-group C.I. + spin-orbit triplet CI from Triplet ground state $END $CONTRL SCFTYP = ROHF RUNTYP = CI ENTTYP = COORD UNITS = ANGS ASYM = C2V INTTYP = 1 APX = INDO/1 NEL = 10 MULT = 3 ITMAX = 40 SCFTOL = .000010 SPNORB = 1 VEC = 9 ! THE ALLOCATION FOR THE CISIZE BELOW = 14, IS AN ESTIMATE OF THE NUMBER ! OF DETERMINANTS NEEDED FOR CALCULATING OSCILLATOR STRENGTH ! IF THIS IS A PROBLEM KEEP UNIT = MOMENTS EXTERNAL DYNAL(1) = 0 0 1 0 1 14 20 ! ***** C.I. size information ***** CISIZE=10 ACTSPC=20 ONAME = CeO1 ! ***** ROHF information ***** NOP = 8 NDT = 0 FOP(1) = 8.000000 1.000000 1.000000 MIM(2) = 7 1 AR(1) = 1.000000 0.000000 1.000000 BR(1) = 1.000000 -1.000000 1.000000 ! ***** Interaction factors ***** INTFA(1) = 1.00000 1.26700 0.58500 1.00000 1.00000 1.00000 ! ***** Beta Values ***** LBETA(1) = 58 8 0 58 58 BETA(1) = -1.00000 -21.00000 00.00000 -6.00000 -12.00000 $END $DATAIN 0.000000 0.000000 0.000000 58 0.000000 0.000000 1.821000 8 $END $CIINPU ! ***** Configuration Interaction specification ***** ! N1 REF ROOTS MULT NATO DEN NOPT FROM->TO FROM->TO 50 1 50 3 0 0 0 1 4 1 50 ! 50=DGCI 1 = 1 REF, 50 states, 3=triplet, 0,0,0 then transition moments ! 1 t0 4 into 1 to 50 (or max number in this case) 0 ! 0 NO THREHOLDS ARE OPERATIVE HERE 4 1 2 3 4 ! THIS IS 4 IRREPS, THE NEXT VALUES ARE ORDER OF COMPONENTS OF ANGULAR ! MOMENT INTEGRALS, AND LEAVE THIS ALONE. THE LAST VALUE IS THE NO OF ! IRREPS CONSIDERED. 58 0.126217 08 0.018846 00 00.000000 58 0.045998 58 0.076995 ! THE ABOVE IS THE RESET OF SPIN ORBIT FACTORS "ZETA" IF DESIRED, THREE P, ! THEN D, THEN F: ATOMIC NUMBER THEN ZETA, IN ATOMIC UNITS ! --------SYMMETRY SET 1 !KSYM NBCFG NCFGIN NCFGDE MXOP KORBOC SEE POWER USERS SECTION 1 1 0 0 2 0 ! SYMMETRY 1, NO. OF BASIC CONFIGS = 1, NO. OF CONFIGS INSERTED, ! No. of CONFIGS DELETED, 2=MAX No. OF OPEN_SHELLS, KORBOC, ! SEE CIGNLS IN POWER USERS SECTION 2222100000010000000011 !<---MO's--------->|<--EXCITATION LEVELS ! FIRST BASIC CONFIGURATION HAS TWO ELECTRONS IN THE FIRST-FOURTH ! MO, THEN 1 IN THE FIFTH AND 1 IN THE 12TH MO. THERE ARE 20 MO'S. ! THERE ARE TWO GROUPS OF EXCITATIONS GIVEN AFTER THIS. ONLY SINGLES ! IN THE FIRST GROUP, AND ONLY SINGLES IN THE SECOND GROUP. THE NEXT ! LINE SPECIFIES THE ACTIVE ORBITAL IN EACH GROUP. ! SEE SUB GENCFG IN POWER USERS SECTION 5 6 7 8 9 10 11 -1 ! THE FIRST GROUP SINGLY EXCITES ALL ORBITALS IN 5-11. NO EXCITATIONS ! IN THE SECOND GROUP. ! 5 6 7 8 9 10 11 12 -2 WOULD BE ALL DOUBLE EXCITATIONS IN THIS GROUP ! OF ORBITALS ! SEE SUB GENCFG IN POWER USERS SECTION !NROOTS ICIWRT 50 1 0 0 0 0 0 ! FOR THE ABOVE SEE CIDG: 50 = MAX NO. OF STATES, THEN ANALYSE THE CI (=1). ! THE OTHER OPTIONS ARE EXPLAINED IN THE POWER USERS SECTION BUT ARE EASILY ! DEFAULTED TO ZERO. -1 0 ! --------SYMMETRY SET 2 2 1 0 0 2 0 2222100000010000000011 5 6 7 8 9 10 11 -1 50 1 0 0 0 0 0 -1 0 ! --------SYMMETRY SET 3 3 1 0 0 2 0 2222100000010000000011 5 6 7 8 9 10 11 -1 50 1 0 0 0 0 0 -1 0 ! --------SYMMETRY SET 4 4 1 0 0 2 0 2222100000010000000011 5 6 7 8 9 10 11 -1 50 1 0 0 0 0 0 -1 0 $END Some comments about output: Some knowledge about the double group will be needed to interpret these results and to assign state symmetries. Recall that for states of half-integral spin (or J) the results that are meaningful occur in irrep #5 of the double group. For integral values of spin (J) the meaningful results occur in the first four irreps; ie, those that would appear in the normal group. ------------------------------------------------------------------- There are two ways to do spin-orbit calculations. The above uses the double group formalism of Pitzer (see Pitzer, Roesch and Zerner). It is effective for small molecules and works over determinants, thus including all possible spin mixings. The second method uses the Rumer formalism of Manne and Zerner as developed by Kotzian, Roesch and Zerner and mixes the spin states of interest with the states of the next highest multiplicity. In the example that follows singlets are mixed with triplets. This is a much faster proceedure. ------------------------------------------------------------------ $TITLEI Rumer CI with spin-orbit on water. ****** NOT FOR EXPORT ******** Configuration Interaction roots E( 1)= -12.34235069 DELTA ENERGY(CM-1)= 0.0 E( 2)= -12.28911576 DELTA ENERGY(CM-1)= 11683.8 E( 3)= -12.27087987 DELTA ENERGY(CM-1)= 15686.1 E( 4)= -12.19520501 DELTA ENERGY(CM-1)= 32294.9 E( 5)= -12.18698504 DELTA ENERGY(CM-1)= 34099.0 E( 6)= -12.16225904 DELTA ENERGY(CM-1)= 39525.8 E( 7)= -12.16175970 DELTA ENERGY(CM-1)= 39635.4 E( 8)= -12.15182784 DELTA ENERGY(CM-1)= 41815.2 E( 9)= -12.14167006 DELTA ENERGY(CM-1)= 44044.6 E( 10)= -12.08022492 DELTA ENERGY(CM-1)= 57530.3 E( 11)= -12.02513743 DELTA ENERGY(CM-1)= 69620.7 E( 12)= -12.01461330 DELTA ENERGY(CM-1)= 71930.4 $END $CONTRL SCFTYP = RHF RUNTYP = CI DYNAL(1) = 0 2 1 0 0 200 80 IAPX = 3 INTTYP = 1 ! SPNORB = 1 FOR RUMER SPIN ORBIT TREATMENT. N1 IN CIINPU = 5 FOR RUMER ! VALENCE BOND CONSTRUCTION, = 105 FOR BRANCHING DIAGRAM CONSTRUCTION. ! (THIS USES A SCHMIDT ORTHOGONALIZATION ON THE RUMER STRUCTURES IN THE ! GENEOLOGICAL ORDER) SPNORB = 1 NAT = 3 NEL = 8 MULT 1 SCFTOL = 0.00001 ITMAX=20 UNITS = BOHR $END $DATAIN 0.000000 0.000000 0.000000 8 0.000000 1.513900 1.171700 1 0.000000 -1.513900 1.171700 1 $END $CIINPU 5 1 20 3 0 0 0 1 1 1 5 -60000.000 0.000000 1 ! THESE RESET SPIN ORBIT ZETA PARAMETERS FIRST THREE ARE P, THEN D THEN F. ! UNITS ARE EV. NOTE O value IS USED HERE BUT THOSE FOR Ce ARE AS EXAMPLES ! LEAVE A LINE OF: ! 0 0.000000 FOR DEFAULT. 58 0.126217 06 0.018846 00 00.000000 58 0.045998 58 0.076995 ! THE NEXT TWO LINES ARE FOR THE TRIPLET CI 1 4 4 21 1 4 5 6 ! THE NEXT TWO LINES ARE FOR THE SINGLET CI 1 4 4 21 1 4 5 6 $END -------------------------------------------------------------------- ---- Section VIII: Power users section ----------------------------- -------------------------------------------------------------------- Additional switches for $CONTRL section ---- Print options ------------------------------------------------- IPRINT = 0 <<<<< for normal operations = 1 ----- Prints H, F, COULOMB, and other calculated matrices =-1 ----- for reduced output. --- Molecular volume and area -------------------------------------- VOLTYPE = GEPOL uses tesserae and gepol93 to calculate surface accessible area and volume. RADTYPE = MASS radius from mass density, default MAXDIM radius from maximum distance/2 + 0.5Angs RAVE radius from average effective distances from center of solute to surface of solvent. If a radius is = 0.0 in the $SCRFIN block, it RADTYPE = MASS is > 0.2 in this block, it overwrites the mass density option and the MAXDIM option, but will be used in RAVE ---- Vectors ------------------------------------------------------- VEC = 0 <<<<< DEFAULT Normal calculation = 8 ----- Read MO coef from file with extnsion .vec8 , first BETA, Then ALPHA = 9 ----- Store MO coef on file with extension .vec9 , Every 5th cycle New vectors will be written in format suitable with reading later using option 8 = 10 ----- Read MO coef from file ONAME.vec8 to start and store MO coef every 5th cycle on file ONAME.vec9 ---- Effective core potential--------------------------------------- VCORE = 1 for the Zerner effective core potential ---- Memory Management --------------------------------------------- DEBUG0 = .TRUE. Print names of subroutines being called to unit 0 = screen. Default = .FALSE. DEBUGM = .TRUE. Print memory allocation and deallocation information Default = .FALSE. MEMINI = .TRUE. Initialize dynamic memory to standard patterns (all reals are 1.23456789012345) Default = .FALSE. ---- Electrostatic potentials -------------------------------------- IELEC = 0 <<<<< DEFAULT = 1 ----- FILE 23 XXXX.inb is cataloged for calculation of electrostatic potentials using ELESTA program ---- Molecular Orbital Plot----------------------------------------- A molecular orbital plot appears below the MO eigenvector printout. This plot can be changed NPLOT = Number of lines in the plot. The default is 50, and this fits on one page of printout. This can be extended up to 200 lines, which is often useful for transition metal complexes which have low lying d orbitals NBELOW = Number of orbital to be shown below HOMO-LUMO gap. The number of virtual orbitals plotted is always 10. The default value is NBELOW = 20; ie, 10 virual and 20 occuppied mo's are plotted on 50 lines. $CONTRL . . NPLOT = 50 NBELOW = 20 . . $END ---- Triplet parameterization -------------------------------------- ITRIP = 0 <<<<< DEFAULT = 1 ----- Triplet parameterization. This is an alternate parameterization. See J.E. Ridley & M. Zerner Theoret. Chim. Acta, 32,111,(1973) Theoret. Chim. Acta, 42,223(1976) ---- Configuration mixing for metals ------------------------------- ISW2 = 0 <<<<< Valence bond mixing of configurations DEFAULT = 1 ----- D(n-1)S(1) configuration of the metal = 2 ----- D(n-2)S(2) configuration of the metal = 3 ----- D(N) configuration of the metal. Only available for the second transition series. = 4 ----- Input extent of configuration mixing First give atomic no. than amount of D(N-2)S(2), then D(N-1)S(1), then D(N) if any. Two sets max in 2(I5,3F10.6) This option has its own group in the data set - The format is I5,%F10.6, and if one line is given, two will be expected. Atomic number, then the five mixing values, and these must add up to 1.000000. For the main transition series COFSQ2(ATOMIC NO., TYPE) TYPE = 1, 2, 3, 4 FOR D(N-1)S(1), D(N-2)S(2), D(N), AND D(N-1)SP RESPECTIVELY. For the lanthanides: TYPE 1 = F(N-3)D S(2) : TYPE 2 = F(N-2) S(2) FOr the actinides: TYPE =1, 5F**(N-3) 6d 7S**2: TYPE=2, 5F**(N-3) 7P 7S**2: TYPE =3, 5F**(N-4) 6d**2 7S**2: TYPE=4, 5F**(N-4) 6d**3 7S: TYPE =5 5F**(N-2) 7S**2 $MIXCOF Z 0.421000 0.220000 0.220000 0.100000 0.040000 <-Atomic number, 0 0.000000 Then the mixing coef. Two lines . are required. $END ---- Output control ---------------------------------------------------- Add a section $OUTPUT, which contains keywords. Various parts of the program print additional information depending on these keywords. Recognized keywords are: ALL Changes the default value for IPRINT to 1. ALL_VARIABLES Prints all variables that the user could have assigned in $CONTRL, no matter whether they actually where input. This is a good way to study the default values. CIMATRICES Prints the CI matrix and the Overlap Matrix between CSF's. CIBONDS Analyzes the bond orders of excited states from N9 to N8 of the CI section, and will also estmate the width of transitions between N1 and N10 thru N11. CIVECTORS Print the entire C.I. vector array. CAREFUL! This may be huge! CONFILE Creates an output file with .con extension and places atomic connection informatino on it. DIHEDRAL Prints all dihedral angles. For a large molecule this could be quite lengthy. DISTANCES Prints the enetire Bond length matrix for each cycle of a geometry search. DIPOLEMAP Prints the dipole matrix elements between CI states. GEOM_ITERATIONS Prints the detailed information on a geometry search. HMATRICES Prints all one-electron matrices MIN Changes the default value for IPRINT to -1. MOS Prints the detailed MO's. This could be lengthy The default prints only the largest components of each MO. NO_OPTFILE By default, Zindo creates an output file with .opt extension and puts geometry optimisation summary in it. By specifying this keyword, the .opt file is deleted at the end of run. OVERLAP Prints the Overlap matrix PCM_DEBUG Prints debug information for the PCM solvent model PCM_VISUAL Prints information from the PCM solvent model, which can be used to visualize the cavity surface and point charges PRNT_SPINDN Calculate and print the spin densities for an ROHF, ROHF/CI or UHF function PUHF_MULPOP Calculate and print the Mullikan population for projected UHF functions. PUHF_NOAISO ? SCF_ITERATIONS Prints additional information about SCF iterations. SUMMARY Prints an one-line summary at the end of run, including SCF energy and dipole moment. Can be useful for processing many output files with 'grep'. SUMRYFILE Creates a file with .smry extension and puts geometry optimisation summary into it. ---- Point charges ------------------------------------------------- $CONTRL . PTCG = N ... $END If point charges are used to modify the one electron matrix, the number of these point charges is N. The coordinates are then given under group as: $PTCHGI A title line of 70 or less symbols - you MUST give a title! The Screening constant (aa) and a bulk dielectric (eps). in 2F10.6. Leave zero if no dielectric screening. A negative value of aa sets e = abs(aa)*R. R in a.u. A zero value of aa, and a value of eps, sets e = eps. Else e = eps -(eps-1)*exp(-aa*R**2) The coordinates in angstroms, X, Y, Z, and the 'atomic no.' of the pt. charge,and the charge, in 3F10.6,I5,F10.6. one pt per line until all pts are given. If the 'atomic no.' is zero a true pt. charge is considered. if not a potential will be generated as if the pt. were an atom of given charge and atomic no. $END For example: $PTCHGI This is a test of point charge option 0.00000 0.00000 <--- aa and eps 0.000000 0.000000 3.000000 0 1.000000 <--- a positive pt. 0.000000 0.000000 -3.000000 0 -1.000000 <--- a negative pt. $END Note that a limited no. of pt. charges can also be added as atoms. In such a case they cannot be screened. ---- Other options --------------------------------------------- AISO = N The magnetic isotropic hyperfine splitting constants will be calculated for state N for ROHF-CI wavefunctions, (The authors favorite method.), or for the HF-SCF reference for the UHF, SUHF and PUHF methods. For the PUHF case the pure S=Ms multiplet is project out of the UHF reference and thus the densities are of those for a proper spin state. (They are variational, but this wave function is no longer stationary with respect to the SCF variational parameters.) (KEYWORD ESR or EPR) NMR = 0 ----- NMR option This is FLORG/LORG and MCZ doesn't like the implementation SPNORB = 0 <<<<< DEFAULT for normal calculations = 1 ----- Spin Orbit calculation will be performed. Both a SINGLET and a TRIPLET CI are required ---- Self Consistent Reaction Field: ------------------------------- ISCRF = 0 <<<<< DEFAULT for normal calculations = 1 ----- Self Consistent Reaction Field. Theory A for the Ground state, theory C for the relaxation of the excited state. = 2 ----- Self Consistent Reaction Field. Theory A for the ground state, but C1 (mean field) for the relaxation of the excited state. = 3 ----- Static electric field or FF = 1 = 4 ----- Our version of the PCM Solvent model. This option enables processing the data block $GEPOL (optional). = 5 ----- SCRF on excited states (Absorbtion spectra) fully relaxed theory, as in ISCRF =2 ,A = 6 ----- SCRF on excited states (Absorbtion spectra) approximate theory, as in ISCRF =1 , B. = 7 ----- SCRF on excited states, mean field, A1 = 8 ----- SCRF on excited states, mean field, B1 = 9 ----- SCRF multicavity, theory A = 10 ---- SCRF multicavity, theory B = 11-14 - Infinite relaxation for absorption- see below. = 15-18 - Infinite relaxation for emission - see below. = 19 ---- SCRF multicavity/ellips, theory C = 20 ---- SCRF multicavity/ellips, theory C1 = 30 ---- reserved for Piet van Duijnen's Direct Reaction Field (not part of current Zindo) If a self consistent reaction field calculation is to be performed then additional information is required, in FORMAT 3I5,6F10.6. ISCRF = As above, repeat this value. NMU = The number of terms in the multipole expansion. Default is 1, the dipole term. IDISP = Is this a calculation for dispersion? If not = 0 no dispersion = 1 the solvent calculation, save the manifold of excited states under SOLNAM_solvent.file. = 2 use the above file in calculating the spectrum of the present solute in the above solvent, including dispersion. A0 = Cavity radius in angstroms: if this is set to zero, mass density will be used to determine A0. EPS = Static dielectric constant for SOLVENT Default = 78.5(water) XND = Refractive index for SOLVENT Default = 1.33287(water) DENSV = Density of the solvent (g/cc), Can be ignored, unless dispersion is calculated. Default = 1.0(water) AMUSV = Molar mass of solvent (amu), Can be ignored, unless dispersion is calculated. No default. DIPSV = Dipole moment of solvent, Can be ignored FNODEN = Solvent reduced number density, from Piorrotti scaled particle theory. This is defaulted to 0.44 (spherical) unless the solvent is water, than 0.371. This value is used to calculated the cavitation energy. If ISCRF = 3 then an addition line is required that contains the field strength in au., with the X, Y, Z components. 1au = 5.14193*10**11 Volts/meter. Formatted as 3F10.6 For example: $CONTRL ... ISCRF = 1 .. $END $SCRFIN 1 2 0 2.000000 78.500000 1.332870<--The solvent is water The cavity of the solute $END molecule has radius 2.0A or $CONTRL ... ISCRF = 3 or FF = 1 .. $END $SCRFIN 3 0.000000 0.000000 0.020000 <----A field of 0.02 a.u. in $END the Z direction or $CONTRL .... ISCRF = 10 .... $END $SCRFIN ISCRF = 10 <--- Theory B for excited states EPS = 3.0 N(D)= 1.414 CAVITY=ELLIPS RHO=1.0 <--- an ellipse, generate shape automatically, assume density equals 1. for the volume. The default cavity type is SPHERE. $END In the $SCRFIN block, Key words may also be used to replace formatted input: a) see above -- summarized First line; in (format 3I5,6F10.6,F5.3) iscrf,nmu,idisp,a0,eps,xnd,densv,amusv,dipsv,fnoden if iscrf=3 then the next line contains as 3f10.6: dipgr(1:3) if iscrf = 11-18, the next line contains as i5: iexstate if idisp =1 or 2, the next line contains an assignment in the form: SOLNAM=XXXXX where XXXXX is the name of the solvent file for dispersion calculation. $SCRFIN 2 2 2 0.000000 2.280000 1.500000 0.876500 78.1100 SOLNAM = benzene $END The above is an example of a calculation in which ISCRF = 2, using dipole and quadropole, default radius of the solute to mass density, dielectric constant, index of refraction, density of the solvent(benzene) = 0.8765, and the molar mass of benzene is 78.11 amu. Note that the benzene_solvent.file is already present, calculated from a previous benzene CI calculation using See RADTYPE below. $SCRFIN 2 2 1 0.000000 2.280000 1.500000 0.876500 78.1100 SOLNAM = benzene $END b) new, names-based version. The general format is the same as for $CONTRL block (Name-value pairs). If the first non-blank character in $SCRFIN is numeric, old format is assumed, else new format is assumed. PLEASE NOTE THAT NOT ALL COMBINATIONS OF KEYWORDS WORK. THE KEY- WORDS MARKED WITH (*) ARE GOOD FOR THE MULTI-CAVITY/ELLIPSOIDAL (THE SCRF-2 PACKAGE, ISCRF=9,10,19,20) ONLY! FF = 0 DEFAULT FF = 1 static field as above. With this option a static electric field and the self consitent reaction field can be simultaneously applied. The ISCRF = anything $SCRFIN 2 2 0 2.000000 78.500000 1.332870<--The solvent is water 0.000000 0.000000 0.001000 The field is 0.001 along z $END The following variable names are recognized in the new format: ISCRF = sets the default value for ISCRF. Please note that: 1) ISCRF in $SCRFIN overrides any value assigned in $CONTRL 2) THEORY, CAVITY, and RELAX are mutually exclusive with ISCRF The recommended practice is to use only ISCRF, _or_ use the combination of the model-specific keywords as described next: THEORY= A B C A1 B1 C1 This sets the basic theory. Default=A CAVITY= SPHERE ELLIPS MULTI PCM This sets the shape of the cavity. Default=SPHERE RELAX= NONE INF-ABS INF-EMI Type of solvent relaxation for solvent calculation. NONE is the default; INF-ABS is for infinite relaxation, absorbtion; INF-EMI is for infinite relaxation, emission. NMOLEC= Number of molecules (fragments, cavities) for the multi-cavity theory; ignored otherwise. NMU= Highest multipole moment to be considered in reaction field. 0=charge only, 1=dipole, 2=quadrupole, 3=octupole, 4=hexa- decapole. default=1 EPS= The dielectric permittivity of the medium. For multi-cavity, this may be input as an array, e.g. EPS(1)=78.5 EPS(2)=30.0 N_D= The index of refraction of the medium. For multi-cavity, this may be input as an array, just like EPS. AMUSV= Molar mass of solvent in a.m.u. RHO= Density of the solute (g/cm**3) DENSV= Density of the solvent (g/cm**3) DIPSV= Dipole moment of the solvent FNODEN= The number density of the solvent, defaults to 0.44 (hard spheres) A0= Radius or radii for the cavity(es). For a single spherical cavity, just the radius. For multi-cavity, input as an array the radii for each cavity: a0(1)=2.5 3.4 6.7 . For ellipsoidal, input the three half-axes in the order (x,y,z) as an array. See also RADTYPE below. FRAG(1)= Array designating atoms to specific fragments. For example, if atoms 1 and 3 belong to fragment 1, and atom 2 belongs to fragment 2, input as FRAG(1)=1 2 1 ALTDEN= A logical value, .T. if an alternate mass-density formula is to be used in cavity size calculations. Default=.F. OVERLAP= A logical value, .T. if cavities are allowed to overlap in multi-cavity model. Default=.F. MULTIPLY= A factor used to multiply all cavity sizes by. This can be used for studies of cavity size; it is applied both to user inputted and to auto-calculated cavities, including the PCM model. Default=1.0 . CENTER= MASS CORE VOLUME - which factor is used to locate the centres of cavities for the multi-cavity & ellispoidal approcahes. Dipole integrals are re-calculated relative to these centers. default=MASS . IDISP= Flag for dispersion calculations: 0 - ignore dispersion (default) 1 - estimate dispersion (calculating solvent) 2 - use dispersion results from a previous run (calcu- lating solute) For options 1 and/or 2 the following data are necessary: SOLNAM= name of the 'solvent file' where information about the states is stored. IEXSTATE= The number of the selected excited state. This is needed for the infinite realaxed models on state IEXSTATE. ---- Polarizable Continuum Model for Solvation ---------------- If the Polarizable Continuum Model for solvation is used, an additional set of keywords is recognized in $SCRFIN. Reminder: ISCRF=4 for PCM. Keywords: LOOP=INSIDE (def) - the surface charges are converged as part if the SCF procedure LOOP=OUTSIDE - looping around calls to SCF procedure in order to converge the charges SELFPOL=.T. (def) - self-polarization is performed SELFPOL=.F. - self-polarization is omitted SELFLOOP=.T. - inside each PCM call, internal loops are used to self-polarize charges SELFLOOP=.F. (def) - the self-polarization of the charges is assumed to take place as part of the overall procedure FIELD=MULLIKEN - use Mulliken charges to generate field This forces LOOP=OUTSIDE FIELD=ZDO - use ZDO charges to generate field FIELD=ZDO+DIP - use ZDO charges + point dipoles to generate field (default) NORMALIZ=BEFORE - charges are renormalized before the self- -polarization procedure is started. NORMALIZ=AFTER(def)-charges are renormalized after being self-polarized. NORMALIZ=NEVER - charges are never renormalized Please note that the default is not to loop around neither inside, use ZDO+dipole field, include self-polarization, and normalize after looping (on every cycle in case of in-loop PCM) Please note that Mulliken charges are available only with loop=outside approach at this time. The additional input block, $GEPOL, may be present to directly interact with the GEPOL93 cavity-generation algorithm. The options are documented in the GEPOL93 manual and source code. No blank lines or free format; the block is scanned starting from the very first line by GEPOL itself. A typical set may include: $GEPOL LPRIN TESSE $END ---- Projected UHF -------------------------------------------- there are 4 additional input switches that append what RUNTYP=PUHF calculates/reports. these are PUHFST and AISO found in the $CONTROL section of the input deck and, PUHF_MULPOP and PUHF_NOAISO found in the $OUTPUT section of the input deck. a stright RUNTYP=PUHF run will output the weights and energies of all multiplets whose weight > 10**(-8), as well as for the unprojected UHF wavefunction. (reguardless of the values of the 4 output control switches the weights and are always reported.) PUHFST: this switch allows the slection of which multiplet/s to analyze by energy. i.e. PUHFST=ABCD will select multiplets AB through CD to be analyzed by energy. e.g. PUHFST=0103=103=0301=301 will cause multiplets 1-3 to be analyzed by energy, or PUHFST=02=2 will cause multiplet 2 to be so analyzed. if PUHFST=-1 then only the weights and are reported. the program default is PUHFST=0 (for larger systems the determination of the energy can be very time consuming, PUHFST is used to eliminate the needless computation of unwanted energies) AISO: this switch selects which multiplets for which the isotropic hyperfine splitting constants will be calculated. it is structured the same as PUHFST, i.e. AISO=ABCD etc., and is independent of the actions of the PUHFST switch. the program default is AISO=0, a negitive value for AISO is the same as AISO=0 PUHF_MULPOP: this switch turns on the mulliken population analysis for the multiplets selected via AISO. i.e. the multiplets selected via AISO will also have their mulliken populations reported. for AISO=0, the default, all mulliken populations will be reported. PUHF_NOAISO: this switch is dependent on both PUHF_MULPOP and AISO being set. i.e. if PUHF_MULPOP is set and AISO.NE.0 then setting PUHF_NOAISO will turn off the determination of the isotropic hyperfine splitting constants. this reduces the amount of unnecessary output. multru below turns on a Mulliken population analysis of the various multiplets it is set via PUHF_MULPOP in the $output section of the input deck: if AISO.NE.0 in the $CONTROL input section then logical AISO is set to .true. and turns on calculation of the isotropic hf splittings: if PUHF_MULPOP and PUHF_NOAISO are found in the $outout section of the input deck then MULISO is set to .false. ---- Resonance Integrals: -------------------------------------- It is possible to alter Beta values for a calculation by using the keywords - LBETA(1) = a1 a2 a3 a4 a5 BETA(1) = sp1 sp2 sp3 d4 f5 The ai are the atomic numbers of the centers to be changed and the spi, di, and fi are the new beta values to be used. Note that the first three positions are reserved for beta(s,p), the fourth for beta(d) and the fifth for beta(f). This option is for ease in reparameterisation of the resonance integral. If the values for a1, a2 or a3 are greater than 1000, the the beta(p) of atomic number (a3 - 1000) is set. i.e. LBETA(1) = 6 1006 0 26 0 BETA(1) = -17.0 -12.0 0.00 -23.0 0.00 or if only one value is changed, can use: LBETA(4) = 26 <----- Iron BETA(4) = -23.0 <----- Beta value for iron in ev. For a more systematic study of parameters there is the For IBETA = 0 (Default) or IBETA = 1 $BETAIN ! s s s s p p p p d d f f ! atomic numbers - THERE MUST BE 12 6 7 0 0 6 7 0 0 0 0 0 0 ! THe 12 beta values corresponing to the above atomic numbers (eV) $END For IBETA = 5 $BETAIN ! s s s s p p p p d d f f ! atomic numbers - THERE MUST BE 12 6 7 0 0 6 7 0 0 0 0 0 0 ! THe 12 beta values corresponing to the above atomic numbers (eV) -17.0 -26.0 -0.00 -0.00 -17.0 -26.0 -0.00 -0.00 -0.00 -0.00 -0.00 -0.00 ! The fkappa values fk(1,1) fk(1,2) fk(2,2): If one value is given, all ! three must be given, else all three are defaulted. 0.000000 0.000000 25.00000 ! the fkappa values fk(1,3) fk(2,3) fk(3,3). If one value is given, all ! three must be given, else all are defaulted. If these values are ! given the previous fk(1,1) fk(1,2) fk(2,2) must have been given. 10.00000 10.00000 25.00000 $END If IBETA = 6, then the exponents and the power can also be added $BETAIN ! First the beta values, B(i) ! ssig s-sig s-sig p-sig p-sig p-sig p-pi p-pi d-sig d-pi d-del ! atomic numbers - there must be 12 6 7 0 6 7 0 6 7 0 0 0 0 ! The 12 beta values corresponding to the above atomic numbers (eV) -17.0 -26.0 -0.00 -17.0 -26.0 -0.00 -17.0 -26.0 -0.00 -0.00 -0.00 -0.00 ! Now the exponents,a(i) ! atomic numbers - there must be 12 6 7 0 6 7 0 6 7 0 0 0 0 ! The 12 exponents corresponding to the above atomic numbers (Bohrs**-1) 0.10 0.10 0.00 0.10 0.10 0.00 0.10 0.10 0.00 0.00 0.00 0.00 ! The M value in H(IJ) = [R**M*(EXP(a(i)+a(j))*R**2)*(B(i)+B(j))/2]* S(ij) 1.00 <---- a floating point number ! If no value above is given it is defaulted to 0.5 ! ! The fkappa values fk(1,1) fk(1,2) fk(2,2): If one value is given, all ! three must be given, else all three are defaulted. 0.000000 0.000000 -25.00000 ! the fkappa values fk(1,3) fk(2,3) fk(3,3). If one value is given, all ! three must be given, else all are defaulted. If these values are ! given the previous fk(1,1) fk(1,2) fk(2,2) must have been given. 10.00000 10.00000 -25.00000 ! the fkappa values fk(1,4) fk(2,4) fk(3,4) and fk(4,4). If one value is ! given, all four must be given, else all are defaulted. If these values are ! given the previous fk(1,3) fk(2,3) fk(3,3) must have been given. -5.000000 -5.000000 -5.000000 -15.00000 $END For testing additional empirical parameters, then the program will read LBETB(1) = a1 a2 a3 a4 a5 BETB(1) = sp1 sp2 p3 d4 f5 The same as it has read LBETA and BETA in the $CONTROL block. See subroutines paramd.f and paramx.f (in file paramd.f) ---- Interaction Factors ---------------------------------------- Generally the interaction factors are defaulted, as given above. The defaults can be overwritten with: INTFA(1) = 1.00 1.267 0.585 1.00 1.00 1.00, etc. as given above. If this is done the order is f, f, f, f, f, f, with all other interactions taken = 1: i.e., f =1.0, etc. For greater fleibility this can be overwritten as FACTR(1) = $CONTRL . . ! INTFA(1) = 1.000 1.2670 0.5850 1.000 1.000 1.000 1.000 FACTR(1) = 1.0 1.00 1.267 1.0 1.0 1.0 1.0 1.0 1.0 1.00 FACTR(11) = 0.0 0.0 1.585 0.0 1.0 1.0 0.0 1.0 1.0 1.0 FACTR(21) = 0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0 1.0 1.0 FACTR(31) = 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0 . . $END The first ten entries are the sigma interactions s-s s-psig psig-psig, s-dsig, psig-dsig, dsig-dsig, s-fsig, etc. The next ten are the pi spi-spi, spi-ppi, ppi-ppi, etc. the first two are dummies The next ten are the delta, the first five are dummies The last ten are phi interactions, only the last is meaningful. ---- Localization: ---------------------------------------------- In the Control Section: LOC = 0 <<<<< DEFAULT for normal calculations > 0 ----- Orbital Localization to be performed (See Below) The occupied orbitals of a molecule may be localized using a Boys, Fermi, or double projector localization. A four digit number controls the localization. DIGIT-1: First occupied localization - (1) BOYS (2) FERMI (3) DOUBLE PROJECTOR (5) BOYS WITH ORBITAL CULL (6) FERMI WITH ORBITAL CULL (7) PROJ. WITH ORBITAL CULL DIGIT-2: Second occ. localization - (1) BOYS (2) FERMI DIGIT-3: First virtual localization - (1) BOYS (2) FERMI (3) DOUBLE PROJECTOR (4) I.V.O. DIGIT-4: Second virt. localization - (1) BOYS (2) FERMI (4) I.V.O. Example: LOC = 3130 = double projector on occ. orbs followed by boys on occ. orbs then double projector on virtual orbs. Orbital cull is set only once, orbitals will be culled for the first and second localization, and any virtual orbital localization. for the boys localization the ci switch (line #1 kci) must be set to 66 if more than 12 orbitals are to be localized using the boys method. both the fermi, double projector localization and orbital culls(removal) need additional data. this data is stored on unit four (name.int), the same unit used FOR internal coordinate data. CULL for an orbital cull Line (1) : ********CLOCAL (*******CLOCALV for the virtual orbitals) Line (2) : # of culling orbitals (I5) Line (3) : orbital range (2I5) Line (4) : # of basis function types in culling orbital, that number OF basis function type numbers. (13I5) Lines (3) and (4) should be repeated as many times as needed. Example: $LOCINP ********CLOCAL <----Line(1) 2 <----Line(2) 1 15 <----Line(3) 3 1 2 3 <----Line(4) 16 17 <----Line(3) 2 1 2 <----Line(4) $END NOTE: This orbital cull will remove orbital(s) OF px,py and pz character from orbitals 1 thru 15, and remove orbital(s) OF px, and py character from orbitals 16 and 17. FERMI for a Fermi localization: Line (1) : ********LOCAL (*******LOCALV for the virtual orbitals) Line (2-N) : X,Y,Z (3F10.6) probe electron coordinates (# OF occupied orbitals - # projected) Example: $LOCINP ********LOCAL <----Line(1) 1.200000 1.000000 2.300000 <----Line(2) Line(2) is repeated as specified above. $END DOUBLE PROJECTOR for a Double Projector localization: Line (1) : ********PLOCAL (*******PLOCALV for the virtual orbitals) Line (2) : # of projected orbitals (I5) Line (3) : # of non-zero basis functions, b.f. #, b.f. coef (I5,4(I5,F10.6)) Line (3A): continue line3 (first field blank) until # of non-zerO basis functions is reached. continue lines (3) and (3a) until # of projected orbitals is reached. Example: $LOCINP ********PLOCAL <----Line(1) 3 <----Line(2) 2 1 1.0 2 1.0 <----Line(3) 5 3 0.3 4 0.4 6 0.6 9 0.9 -Line(3) 10 0.8 <---Line(3a) 1 11 1.0 <----Line(3) $END In the above example three mo's are projected from those that are occuppied. The first sought is that which is most like a 50%-50% mix of a.o.'s 1 and 2, the next is an m.o. that is 0.3 a.o. #2, 0.4 a.o. #4, etc., and the last m.o. is as pure a.o. 11 as can be projected. The remaining orbitals not projected are as much like the original canonical m.o.'s as possible, with those specified projected out. ---- Dipole integrals ------------------------------------------------- In the $CONTRL block DIPOLE = 1, is the default, and the dipole moments are calculated with the one center charge and polarization integrals. DIPOLE = 2, The dipole integrals are calculated including the two- center bond terms, and these integrals are then sym. orthogonalized if a ZDO model is used. DIPOLE = 3, Only the one center diagonal (or charge term) is used. DIPOLE =11,12,13 as above, but quadropole moment is also calculated ---- Fragment Orbital Analysis: --------------------------------------- First run the composite (super) molecule. This will require In the $CONTRL block: FRAG = 0 <------ If none. This is the default. = 1 this is a fragment orbital calculation = 2 the fragment being calculated is an atom. Additional input required. Then a FRAGIN block is required. $FRAGIN free ethylene <--- a title ethyl <-- The name of the data for the composite molecule that will be analized into fragments. This is the ONAME of this job, and will produce a file called "ethyl.frag" methyl1 <--- the name of the first fragment, and this must be the ONAME of the ZINDO job that runs this fragment. The output for the fragment analysis will be methyl1.frag. methyl2 <--- the name of the second fragment: Give the names of all fragments $END NOTE: The composite (larger) molecule must be the first parameter and the fragments must follow in the same order as they do in the composite molecule. This first job will output a ONAME.PMO (or, as above, ethyl.PMO). Then each fragment must be calculated, with the same coordinates as in the composite molecule. In the control block, FRAG =1 or 2 (see below) and the FRAGIN block needs only a title. Each run will produce a ONAME.frag file. These names must agree with those supplied in the FRAGIN block of the initial run. If a fragment is a single atom then the switch must be 2, this will ensure that the aos are in the correct order. Otherwise use 1. The actual fragment analysis is done by a separate program called frganl.f. It uses some files generated by the ZINDO program. Once you have obtained .frag files for the molecule and all of its fragments you can start the analysis by entering frganl < (moleculename).PMO Output will appear in a file ONAME.fmout where ONAME is that of the compound molecule. example: Job 1. $TITLEI ethylene fragment test $END $CONTRL SCFTYP RHF RUNTYP ENERGY ENTTYP COORD UNITS ANGS INTTYP 1 IAPX 3 NAT 6 NEL 12 MULT 1 ITMAX 30 FRAG 1 SCFTOL 0.000200 ONAME = ethyl $END $DATAIN -2.000000 0.645000 0.000000 6 -2.000000 1.190000 -0.943968 1 -2.000000 1.190000 0.943968 1 -2.000000 -0.685000 0.000000 6 -2.000000 -1.230000 0.943968 1 -2.000000 -1.230000 -0.943968 1 $END $FRAGIN ! ***** Molecular fragmentation specification ***** free ethylene ethyl methyl1 methyl2 $END Job 2. $TITLEI meth1 first fragment $END $CONTRL SCFTYP RHF RUNTYP ENERGY ENTTYP COORD UNITS ANGS INTTYP 1 IAPX 3 NAT 3 NEL 6 MULT 1 ITMAX 30 FRAG 1 SCFTOL 0.000200 ONAME = methyl1 $END $DATAIN -2.000000 0.645000 0.000000 6 -2.000000 1.190000 -0.943968 1 -2.000000 1.190000 0.943968 1 $END $FRAGIN ! ***** Molecular fragmentation specification ***** free ethylene methylene $END Job 3. $TITLEI meth2 second fragment $END $CONTRL SCFTYP RHF RUNTYP ENERGY ENTTYP COORD UNITS ANGS INTTYP 1 IAPX 3 NAT 3 NEL 6 MULT 1 ITMAX 30 FRAG 1 SCFTOL 0.000200 DYNAL(1) = 0 2 1 0 0 0 0 ONAME = methyl2 $END $DATAIN -2.000000 -0.685000 0.000000 6 -2.000000 -1.230000 0.943968 1 -2.000000 -1.230000 -0.943968 1 $END $FRAGIN ! ***** Molecular fragmentation specification ***** free ethylene methylene $END Job 4. frganl < ethyl.PMO & ---- Memory Management ------------------------------------------------ By default, the program attempts to grab as much memory as possible for various arrays, and internal I/O files. In many situations this may not be desirable. In such situations the user can limit the available memory by specifying MEMORY= in the $CONTRL block. This puts an upper limit (in bytes) on the memory the program can use. Please note that the executable itself, and statically allocated arrays take about 12 megabytes (possibly more in the future), which comes in addition to the amount allowed by MEMORY switch. Various I/O units can also be either stored in the memory or on disk. The default is always in memory, if there is memory available. If there is a shortage of memory, the user can make possibly better choices than the primitive priority-based algorithm in fileop.f . For such purpose, add the block $EXTERN into the input file, and list the names of the units (omitting the initial IO_ and possibly some characters from the end - see program output!) which can be made external. The keyword 'ALL' makes all units external, thus conserving the most of memory. Please note that the latter may also make the program very slow. For more information about the I/O units, see programmers manual, units.doc, and study the relevant sections of output. ---- Self Consistent Field Convergence --------------------------------- In general, the SCF is accelerated by using the dynamic damping of Zerner and Bacon, and Zerner and Hehenberger. If the program detects a problem with convergence, the DIIS method of Pulay is switched on. The default value for the DIIS to be put into operation is when the DIFF in the energy from cycle to cycle is less than 10**(-7) Hartrees. The default is equivalent to DIIS = -7 in the $CONTRL section. This value can be changed: ie, DIIS = -6 <--- when DIFF = 10**(-6) start DIIS procedure. etc. IDD2 = 0 will shut the DIIS option off. This is often a good idea if the self consistent field calculation does not converge. ---- Spin Orbit Double Group ------------------------------------------ These are the switches defined in subroutine CIDG see above example of double group CI. NROOTS NUMBER OF ROOTS OF THE CI MATRIX ICIWRT CI WRITE OPTION ICIWRT = 0 PRODUCTION RUN, MINIMUM OUTPUT = 1 PRINTS ALL OF CI VECTORS = 2 PRINTS THE CI MATRIX = 3 PRINTS THE COMPLETE LIST OF CI DATA ICIPUN CI PUNCH OPTION ICIPUN = 0 DO NOT WRITE THE CI VECTORS = 1 WRITE THE CI VECTORS ON IUNT2B INTWRT INTEGRAL WRITE OPTION INTWRT = 0 PRODUCTION RUN, MINIMUM OUTPUT = 1 WRITES OUT THE ONE-ELECTRON INTEGRALS = 2 CALLS ANALYZ TO PERFORM PERTURBATIVE ENERGY ANALYZATION --------- ORIGINALLY: = 2 WRITES OUT THE ONE- AND TWO- ELECTRON INTEGRALS IHAMRD HAMILTONIAN READ OPTION IHAMRD = 0 THE HAMILTONIAN MATRIX IS COMPUTED = 1 THE HAMILTONIAN MATRIX IS READ IN FROM IUNT2A IANALZ VECTOR AND ENERGY STATISTICS OPTION IANALZ = 0 NO VECTOR OR ENERGY BREAKDOWN = 1 PROVIDE VECTOR AND ENERGY BREAKDOWN MAXNE0 MAXIMUM NUMBER OF NONZERO HAMILTONIAN MATRIX ELEMENTS PER ROW; IGNORED UNLESS IHAMRD = 1, IN WHICH CASE THE VALUE IS OBTAINED FROM THE PREVIOUS RUN'S OUTPUT This ends the data on this line. KSYM DOUBLE-GROUP SYMMETRY OF STATE KSYM = 1 TO 5 FOR C2V, D2 KSYM = 1 TO 10 FOR D2H NTOTFG NUMBER OF SPATIAL CONFIGURATIONS ---- Historical switches (Probably not functional) --------------------- ISAVE = 0 <<<<< DEFAULT Normal calculation = 1 ----- Save ground state on tape unit 14 = 2 ----- Recall ground state calc from tape for CI, unit 14 (Unit 14 and Unit 16 must be cataloged data sets!) = 3 ----- Recall ground state calc. as above, and recover transformed integrals from Unit 2 (direct access) = 4 ----- Recall 1 AND 2 Electron files and calculate electroni energy. Unit 11 and Unit 16 Must be saved. = 5 ----- AB INITIO........... Recall 1 and 2 electron files from MOLECULE program and calculate electronic energy. Unit 8 (MOLECULE integrals) must be saved. IPUN = 0 <<<<< DEFAULT Normal calculation = 1 ----- Punch charge and bond order matrix (Unit 7) = 2 ----- Read previous density matrix to start iteration = 3 ----- Read previous density matrix to start iteration and punch the calculated density matrix (Unit 7) -------------------------------------------------------------------- ---- Some program arrays ------------------------------------------- -------------------------------------------------------------------- NEL = Number of electrons in the molecule NB = Number of basis orbitals EIG = Eigenvalue vector C(I,J) = Matrix of eigenvectors, the I-th AO in the J-th MO is stored as C(L) where L=I+J(J-1)*NB NU(I) = Atom to which the I-th orbital belongs NW(I) = Type of atomic basis orbital of I-th Atomic orbital CO(J,I) = Coordinates of atom I NTYP(I) the type of I-th atom TYPE=1 for nS basis =2 for nS,nP basis =3 for nS,nP,nD basis =4 for nS,nP,(n-1)D basis. =5 for nS,nP,(n-1)D,(n-2)F NP(I) = Principal quantum number of I-th atomic orbital ALPHA(I,J)=J-th orbital exponent of I-th AO J=4-6 expansion coefficient for I-th AO NA=Number of atoms KAN(I) = Atomic number of I-th atom -------------------------------------------------------------------- ---- Control words and data blocks --------------------------------- -------------------------------------------------------------------- The following describes the structure of the blocks in the data set. Note that most of them require the data in format once the data begins. That is, you can not put comments in the middle of the cartesian coordinates for example. The INPUT deck. col 12345678 BLOCKS: |$XXXXXX | |NAME'separator'VALUE(S) | | valid 'separator' is an equal (=) sign | or a space ( ). | |ARRAYS are NAME(IND)'separator'a b c ... where | NAME(IND) = a, | NAME(IND+1) = b, etc | |LOGICAL VALUES are .TRUE. .FALSE. | |COMMENTS begin with "!", go to the | end of the line and can occur | anywhere in the INPUT deck, except | inside of a bunch of formatted data. | |$END The BLOCK descriptor, $XXXXXX, must begin in column 2, NAMES can occur anywhere followed by VALUES. Here is a list of all WORDS which are recognized by the NAME directed input routine of ZINDO and should be in the $CONTRL group. (THE FOLLOWING LIST IS OUTDATED AND SHOULD BE CONSIDERED HISTORICAL) Logicals: LMASS -| LEXACT | Geometry Optimization LINV -| Integers: DYNAL( ) - Basis set definition + C.I. spec. PUN VEC - Read or save vectors IDD1 =9 Calculates the kinetic energy =1 Calculates the electron-nuclear attraction explicitly. IDD2 .ne. 0 => DIIS is possible. IBETA =0 Sum form for beta,default. =1, product form for beta =2, sum form with a+b/R =3, product form with a+b/R =5, beta is of pair type. =6, beta = r**n(exp(a*r**2)*betave INTTYP - Integral type IAPX - Approximate theory III -| MODE | Geometry Optimization ITYPE | ISRCH -| IPRINT - Print switch NAT - number of atoms NEL - number of electrons IELEC - electrostatic potentials MULT - multiplicity ITRIP - triplet parametrization ISW2 - type of configuration mixing ICHARG NMR - nmr option PTCG - number of point charges SPNORB - spin orbit option ITMAX - maximum number of iterations DIIS - scf convergence needed before DIIS is used ISCRF - self consistent reaction field NMU - scrf LOC - localization FRAG - molecular fragmentation NOP - number of open shell orbitals. NDT - default coupling constants for ROHF or not MIM( ) - total number of orbitals per open shell LBETA( ) - atomic number of atom for new betas POLAR - the switch for calculating polarizabilities. DIPOLE - 1=Default=1-center integrals,2=two-center integrals. Reals: SCFTOL - convergence criteria RHO -| SIGMA | Geometry optimization PHASE | STPTOL | STPTLD -| A0 -| EPS | XND | Self consistent reaction field RHO | AMUSV | DIPSV | DIGPR( )-| INTFA( ) - interaction factors FOP( ) - number of closed shell electrons, # e/open shell AR( ) - alpha coupling contants BR( ) - beta coupling constants BETA( ) - new beta parameters Characters: SCFTYP - RHF etc RUNTYP - ENERGY etc ENTTYP - atomic coordinates or zmatrix UNITS - angstroms or bohr ASYM - molecular symmetry ONAME - output file name FNAME - fragment name Recognized BLOCKS in the data set are - $TITLEI $CONTRL $DATAIN - formatted $CIINPU - formatted $ASSINP - formatted $LOCINP - formatted $FIXCOR - formatted $MIXCOF - formatted $PTCHGI - formatted $FRAGIN - formatted $SCRFIN - formatted ------------------------------------------------------------------- -------------------------------------------------------------------