From owner-chemistry@ccl.net Wed Dec 14 06:38:00 2011 From: "=?Windows-1252?Q?J=FCrgen_Gr=E4fenstein?= jurgen:-:chem.gu.se" To: CCL Subject: CCL:G: CASSCF problems Message-Id: <-46030-111214061008-3044-pCLu+6gKjFDIg5igb/zJAQ-#-server.ccl.net> X-Original-From: =?Windows-1252?Q?J=FCrgen_Gr=E4fenstein?= Content-Language: en-US Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset="Windows-1252" Date: Wed, 14 Dec 2011 11:09:57 +0000 MIME-Version: 1.0 Sent to CCL by: =?Windows-1252?Q?J=FCrgen_Gr=E4fenstein?= [jurgen{:}chem.gu.se] Dear Thomas, I suppose you mix up NO with the situation in O_2. In O_2, you have two electrons in the (antibonding) pi orbitals. Here, DFT/HF are unable to properly describe the singlet states. None of the configurations (pi_x_alpha+pi_x_beta, pi_y_alpha+pi_y_beta, pi_x_alpha+pi_y_beta, pi_y_alpha+pi_x_beta ) are eigenfunctions to the L_z operator. Rather, the mentioned configurations have to be combined to form (i) one component of the ^3\Sigma_g^– multiplet (the other two being pi_x_alpha+pi_y_alpha and pi_x_beta+pi_y_beta), (ii) a ^1\Sigma_g^+ state, and (ii) a pair of ^1\Delta_g states. (Sorry for the inconsistent notation, I hope it works!) In NO, on the contrary, you have just one electron in the antibonding pi orbitals. This electron may sit in either pi_x or pi_y (or "tilted"). The many-particle state of NO is thus degenerate (^2\Pi) not only with respect to spin but also with respect to the L_z value (+1 or -1, alternatively Pi_x or Pi_y). Any wavefunction for that state will break rotational symmetry around the axis of the molecule. Thus, in this case the essence of the HF/DFT MO picture survives the inclusion of non-dynamical correlations. To restore rotational symmetry around the molecular axis, you have to merge Pi_x and Pi_y states into a mixed state, which needs to be described by a many-electron density matrix rather than a wavefunction. It is this mied state that is descried by FON-DFT or state-averaged CASSCF. As for the optimization, Gaussian should provide a full 2nd-order algorithm. There may be no keyword to invoke it, so you need to specify an option. In G03, it was IOp(5/17=100). Please be advised, however, that I have little to no experience with tricky CASSCF optimizations. Best regards, Jürgen Sent to CCL by: Thomas Exner [thomas.exner*|*uni-konstanz.de] Dear Jürgen: Thank you very much for pointing me to the FON-DFT approach. I will definitely look into it. But I still think that standard CASSCF should be able to get it right. Perhaps I make a complete fool out of me, anyway: In an MO picture, there are the two degenerated states (pi_x and pi_y) and HF and DFT, which take no non-dynamic correlation into account, should convert to one of these. But the NO molecule should show a symmetric electron distribution, which shows, in my opinion, that the MO scheme is misleading. Fractional occupation numbers help here, since one can put half an electron in each of the two degenerated pi orbitals. But is that not exactly what CASSCF is meant for. By combining multiple electron configurations, the calculation should be able (in a very simplified way to demonstrate my point) to take the two configuration with the unpaired electron in the pi_x orbital and in the pi_y orbital, respectively, with equal contribution. This would then result in an electron occupation of 0.5 in both orbitals, exactly what I expect. Any comments on that or a reason, why I am wrong? And, really no suggestions for my second question? "Additionally, I have a larger system for which I also perform casscf calculations. Ground state simulations and also the first excited state using the ground state geometry are fine. Energy optimization in the excited state also starts ok but after some steps the calculation does not converge anymore. Use of "use=l506" as proposed in the g09 manual did not help. Also no luck with increasing the maxcycle or starting with an other conformation. Is there anything else I can try? Perhaps there are some options for the optimizer that he does not jump into the bad region with the convergence problems. Unfortunately, the "sleazy" and the "qc" keyword for scf cannot be used with casscf optimization." Thanks. Thomas From owner-chemistry@ccl.net Wed Dec 14 10:20:01 2011 From: "Djordje Francuski djordjef:imgge.bg.ac.rs" To: CCL Subject: CCL: Sulfur basis set Message-Id: <-46031-111214092920-27552-Meeuiruwx+L00SgORBgwGg]![server.ccl.net> X-Original-From: "Djordje Francuski" Content-Transfer-Encoding: 8bit Content-Type: text/plain;charset=utf-8 Date: Wed, 14 Dec 2011 15:29:05 +0100 (CET) MIME-Version: 1.0 Sent to CCL by: "Djordje Francuski" [djordjef(a)imgge.bg.ac.rs] Dear CCL subscribers, I am trying to theoretically model the deformation density in thiosemicarbazide, concentrating on the density around sulfur. I am using the Crystal09 program and basis sets from the Basis set exchange. I hoped more complex Basis sets than 6-21 might bring up the deformation density around sulfur, as I see it in experimental data, but there is not much improvement there. I am hoping someone has an advice if applying more complex basis sets would yield better results in this case and which basis set I should try? I already tried 6-311G* but without much improvement. Looking through the archive on the ccl page I found only people asking about an appropriate sulphur basis set but no hint on which one to use. Any paper you might suggest for reading on the subject of sulfur basis set would be also welcome. Thanks in advance, Djordje From owner-chemistry@ccl.net Wed Dec 14 10:54:01 2011 From: "Jason D Acchioli jdacchio]*[gmail.com" To: CCL Subject: CCL: Sulfur basis set Message-Id: <-46032-111214104429-10489-uYbbINyfkHbuVuB4TN8kjg+/-server.ccl.net> X-Original-From: "Jason D'Acchioli" Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=us-ascii Date: Wed, 14 Dec 2011 09:44:13 -0600 Mime-Version: 1.0 (Apple Message framework v1251.1) Sent to CCL by: "Jason D'Acchioli" [jdacchio###gmail.com] Djordje, You also need to worry about diffuse functions on sulfur. A 6-31+G* or 6-311+G* would be better choices. Best wishes, Jason On Dec 14, 2011, at 8:29 AM, Djordje Francuski djordjef:imgge.bg.ac.rs wrote: > > Sent to CCL by: "Djordje Francuski" [djordjef(a)imgge.bg.ac.rs] > Dear CCL subscribers, > > I am trying to theoretically model the deformation density in > thiosemicarbazide, concentrating on the density around sulfur. > I am using the Crystal09 program and basis sets from the Basis set > exchange. I hoped more complex Basis sets than 6-21 might bring up the > deformation density around sulfur, as I see it in experimental data, > but there is not much improvement there. > I am hoping someone has an advice if applying more complex basis sets would > yield better results in this case and which basis set I should try? I > already tried 6-311G* but without much improvement. > > Looking through the archive on the ccl page I found only people asking about > an appropriate sulphur basis set but no hint on which one to use. > Any paper you might suggest for reading on the subject of sulfur basis set > would be also welcome. > > Thanks in advance, > Djordje> > ******************************************* Jason D'Acchioli Assistant Professor of Chemistry University of Wisconsin-Stevens Point 2001 Fourth Avenue Stevens Point, WI 54481 http://chemdac.uwsp.edu From owner-chemistry@ccl.net Wed Dec 14 11:30:00 2011 From: "dipankar roy theodip-,-gmail.com" To: CCL Subject: CCL: Sulfur basis set Message-Id: <-46033-111214110454-11066-u4B0PqQ2KRuTNKuZzGQVWQ-$-server.ccl.net> X-Original-From: dipankar roy Content-Type: multipart/alternative; boundary=00032555606293f5da04b40f8636 Date: Wed, 14 Dec 2011 11:04:41 -0500 MIME-Version: 1.0 Sent to CCL by: dipankar roy [theodip[#]gmail.com] --00032555606293f5da04b40f8636 Content-Type: text/plain; charset=windows-1252 Content-Transfer-Encoding: quoted-printable Hi, The following may be of some help J. Chem. Theory Comput., 2005, 1 (5), pp 900=96907 J. Chem. Phys. *108*, 2791 (1998) best, Dipankar Roy ----------------------------------- Dr. Dipankar Roy Research Associate Hunter College (CUNY) 695 Park Avenue New York, USA NY-10065 ----------------------------------- On Wed, Dec 14, 2011 at 9:29 AM, Djordje Francuski djordjef:imgge.bg.ac.rs = < owner-chemistry###ccl.net> wrote: > > Sent to CCL by: "Djordje Francuski" [djordjef(a)imgge.bg.ac.rs] > Dear CCL subscribers, > > I am trying to theoretically model the deformation density in > thiosemicarbazide, concentrating on the density around sulfur. > I am using the Crystal09 program and basis sets from the Basis set > exchange. I hoped more complex Basis sets than 6-21 might bring up the > deformation density around sulfur, as I see it in experimental data, > but there is not much improvement there. > I am hoping someone has an advice if applying more complex basis sets wou= ld > yield better results in this case and which basis set I should try? I > already tried 6-311G* but without much improvement. > > Looking through the archive on the ccl page I found only people asking > about > an appropriate sulphur basis set but no hint on which one to use. > Any paper you might suggest for reading on the subject of sulfur basis se= t > would be also welcome. > > Thanks in advance, > Djordje > > > > -=3D This is automatically added to each message by the mailing script = =3D-> > > --00032555606293f5da04b40f8636 Content-Type: text/html; charset=windows-1252 Content-Transfer-Encoding: quoted-printable Hi,
The following may be of some help

J. Chem. Theory Comput.,=A02005,=A01=A0(5), pp 900=96907=
J. Chem. Phys.=A0, 2791 (1998)

<= span class=3D"Apple-style-span" style=3D"font-family:arial,sans-serif;font-= size:12px;text-align:-webkit-auto;background-color:rgb(255,255,255)">best,<= /span>
Dipankar Roy

----= -------------------------------
Dr. Dipankar Roy
Research Associate
Hunter College (CUN= Y)
695 Park Avenue
New York, USA
NY-10065
-----------------------------------


On Wed, Dec 14, 2011 at 9:29 AM, Djordje Francus= ki djordjef:imgge.bg.ac.rs <owner-chemistry###ccl= .net> wrote:

Sent to CCL by: "Djordje Francuski" [djordjef(a)imgge.bg.ac.rs]
Dear CCL subscribers,

I am trying to theoretically model the deformation density in
thiosemicarbazide, concentrating on the density around sulfur.
I am using the Crystal09 program and basis sets from the Basis set
exchange. I hoped more complex Basis sets than 6-21 might bring up the
deformation density around sulfur, as I see it in experimental data,
but there is not much improvement there.
I am hoping someone has an advice if applying more complex basis sets would=
yield better results in this case and which basis set I should try? I
already tried 6-311G* but without much improvement.

Looking through the archive on the ccl page I found only people asking abou= t
an appropriate sulphur basis set but no hint on which one to use.
Any paper you might suggest for reading on the subject of sulfur basis set<= br> would be also welcome.

Thanks in advance,
Djordje



-=3D This is automatically added to each message by the mailing script =3D-=
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--00032555606293f5da04b40f8636-- From owner-chemistry@ccl.net Wed Dec 14 12:59:01 2011 From: "=?iso-8859-2?Q?=22Kacper_Dru=BFbicki=22?= kacper.druzbicki%a%uj.edu.pl" To: CCL Subject: CCL: Sulfur basis set Message-Id: <-46034-111214125806-19068-LT4yUGJDIkR05ykvq1/dug|a|server.ccl.net> X-Original-From: =?iso-8859-2?Q?=22Kacper_Dru=BFbicki=22?= Content-disposition: inline Content-language: en Content-Transfer-Encoding: 8bit Content-type: text/plain; charset=iso-8859-2 Date: Wed, 14 Dec 2011 18:57:56 +0100 MIME-version: 1.0 Sent to CCL by: =?iso-8859-2?Q?=22Kacper_Dru=BFbicki=22?= [kacper.druzbicki]^[uj.edu.pl] Hello, > You also need to worry about diffuse functions on sulfur. A 6-31+G* > or 6-311+G* would be better choices. As I remember it is advised against using diffuse functions in CRYSTAL. In the dense packed systems, the diffuse fuctions may lead to huge basis set superposition errors due to their overlaping and deliver big numerical troubles. There is also some info in the CRYSTAL manual, that the extended basis sets should be avoided for the similar reason. http://www.tcm.phy.cam.ac.uk/~mdt26/crystal.html Following the link, you can find something about CRYSTAL basis sets along with some info about their oprimization. Maybe you should rather try to direct your question to Dr Towler or to the CRYSTAL support team? Greetings, Casper Kacper Dru¿bicki, Faculty of Chemistry, Department of Chemical Physics, Jagiellonian University, Ingardena Street 3, 30-060 Cracow, Poland phone: +48 12 6632265 ----- Original Message ----- > From: "Jason D Acchioli jdacchio]*[gmail.com" Date: Wednesday, December 14, 2011 6:20 pm Subject: CCL: Sulfur basis set To: "Druzbicki, Kacper " > Sent to CCL by: "Jason D'Acchioli" [jdacchio###gmail.com] > Djordje, > > You also need to worry about diffuse functions on sulfur. A 6-31+G* > or 6-311+G* would be better choices. > > Best wishes, > > Jason > > On Dec 14, 2011, at 8:29 AM, Djordje Francuski djordjef:imgge.bg.ac.rs > wrote: > > > > > Sent to CCL by: "Djordje Francuski" [djordjef(a)imgge.bg.ac.rs] > > Dear CCL subscribers, > > > > I am trying to theoretically model the deformation density in > > thiosemicarbazide, concentrating on the density around sulfur. > > I am using the Crystal09 program and basis sets from the Basis set > > exchange. I hoped more complex Basis sets than 6-21 might bring up the > > deformation density around sulfur, as I see it in experimental data, > > but there is not much improvement there. > > I am hoping someone has an advice if applying more complex basis > sets would > > yield better results in this case and which basis set I should try? > I > > already tried 6-311G* but without much improvement. > > > > Looking through the archive on the ccl page I found only people > asking about > > an appropriate sulphur basis set but no hint on which one to use. > > Any paper you might suggest for reading on the subject of sulfur > basis set > > would be also welcome. > > > > Thanks in advance, > > Djordje> > > > > ******************************************* > Jason D'Acchioli > Assistant Professor of Chemistry > University of Wisconsin-Stevens Point > 2001 Fourth Avenue > Stevens Point, WI 54481 > http://chemdac.uwsp.edu> > From owner-chemistry@ccl.net Wed Dec 14 15:50:00 2011 From: "Adam Joseph Simbeck simbea:rpi.edu" To: CCL Subject: CCL:G: G03 Fock/Overlap Matrices using HUCKEL Message-Id: <-46035-111214132217-7944-guFLo9w61QSNz4kIg22jyg[#]server.ccl.net> X-Original-From: "Adam Joseph Simbeck" Date: Wed, 14 Dec 2011 13:22:16 -0500 Sent to CCL by: "Adam Joseph Simbeck" [simbea]-[rpi.edu] Hi All, This is my first time posting. I am attempting to get both the Fock and Overlap matrices from Gaussian 03 for H2. I know that there are two primary ways to do this. The first is to use the IOp keyword and the overlay numbers. For example, IOp(5/33=3,3/33=5) will print the Fock and overlap matrices in the log file. The second method is to save the rwf file by adding %rwf=file.rwf to the com file and using rwfdump with the appropriate rwf numbers, specifically 514, 536, and 538 (I think), to get the Overlap and Fock matrices. For example, one could type the command: rwfdump file.rwf out-file 514r to get the Overlap matrix. By replacing 514 with 536 and 538 one can then print the alpha and beta Fock matrices. Both of these methods work just fine and give identical results for H2 when I use the following method/basis set combination: UB3LYP/6-31G(d,p). My generic input appears as follows: %chk=h2.chk %mem=1gb %nprocs=4 #P UB3LYP/6-31G(d,p) Test SCF of H2, dump H/S matrices 0 1 H 0.0 0.0 -0.37145 H 0.0 0.0 0.37145 If I use HUCKEL instead of UB3LYP/6-31G(d,p) though, neither method for printing the Overlap/Fock matrices appears to work. So my question is how to use the HUCKEL keyword and still be able to print the Overlap/Fock matrices? My understanding of the HUCKEL keyword is very naive so I apologize if my mistake is something simple that I am missing. Thanks for your responses in advance. Adam J. Simbeck simbea_+_rpi.edu Rensselaer Polytechnic Institute 110 Eighth Street, Troy, NY 12180 From owner-chemistry@ccl.net Wed Dec 14 16:25:00 2011 From: "Adam Joseph Simbeck simbea,,rpi.edu" To: CCL Subject: CCL:G: G03 Fock/Overlap Matrices using HUCKEL Message-Id: <-46036-111214131211-1266-gZpXEmPpgqrQNFY3DBy5tQ+*+server.ccl.net> X-Original-From: "Adam Joseph Simbeck" Date: Wed, 14 Dec 2011 13:12:10 -0500 Sent to CCL by: "Adam Joseph Simbeck" [simbea**rpi.edu] Hi All, This is my first time posting. I am attempting to get both the Fock and Overlap matrices from Gaussian 03 for H2. I know that there are two primary ways to do this. The first is to use the IOp keyword and the overlay numbers. For example, IOp(5/33=3,3/33=5) will print the Fock and overlap matrices in the log file. The second method is to save the rwf file by adding %rwf=file.rwf to the com file and using rwfdump with the appropriate rwf numbers, specifically 514, 536, and 538 (I think), to get the Overlap and Fock matrices. For example, one could type the command: rwfdump file.rwf out-file 514r to get the Overlap matrix. By replacing 514 with 536 and 538 one can then print the alpha and beta Fock matrices. Both of these methods work just fine and give identical results for H2 when I use the following method/basis set combination: UB3LYP/6-31G(d,p). My generic input appears as follows: %chk=h2.chk %mem=1gb %nprocs=4 #P UB3LYP/6-31G(d,p) Test SCF of H2, dump H/S matrices 0 1 H 0.0 0.0 -0.37145 H 0.0 0.0 0.37145 If I use HUCKEL instead of UB3LYP/6-31G(d,p) though, neither method for printing the Overlap/Fock matrices appears to work. So my question is how to use the HUCKEL keyword and still be able to print the Overlap/Fock matrices? My understanding of the HUCKEL keyword is very naive so I apologize if my mistake is something simple that I am missing. Thanks for your responses in advance. Adam J. Simbeck simbea###rpi.edu Rensselaer Polytechnic Institute 110 Eighth Street, Troy, NY 12180