CCL:G: Different single-point DFT energy between GAMESS and Gaussian



The most likely scenario is the basis set linear dependency. GAMESS remove
 the linear dependent (or more precisely, the near linear dependent) component in
 the basis set space. This certainly will slightly change the energies. Here is
 an example output from GAMESS. You can check your log file for similar
 information:
  
  NUMBER OF CARTESIAN ATOMIC
 ORBITALS=        166
  NUMBER OF SPHERICAL CONTAMINANTS DROPPED=     0
  NUMBER OF LINEARLY DEPENDENT MOS DROPPED=     2
  TOTAL NUMBER OF MOS IN VARIATION SPACE=     164
  THE INPUT BASIS SET CONTAINS APPROXIMATE LINEAR DEPENDENCE.
  THE SMALLEST EIGENVALUE OF THE OVERLAP MATRIX IS   2.898259E-09
  THERE ARE    2 EIGENVALUES LESS THAN QMTTOL=  1.00E-07
  EIGENVECTORS BELOW -QMTTOL- ARE DROPPED FROM THE MO SPACE,
  IN ORDER TO ELIMINATE THE APPROXIMATE LINEAR DEPENDENCE.
  THIS WILL MOST LIKELY CHANGE THE ENERGY ON THE ORDER OF TENS OF
 MICROHARTREES,
  DEPENDING ON THE NUMBER OF ORBITALS REMOVED.  THE VALUE OF QMTTOL CAN
 BE
  CHANGED IN $CONTRL: JOBS WITH EIGENVALUES BELOW 1.0E-07 PROBABLY WON'T
  CONVERGE.  EIGENVALUES BETWEEN 1.0E-07 AND 1.0E-06 MAY REQUIRE
 LOOSENING OF
  THE DENSITY CRITERION (CONV IN $SCF), MORE ACCURATE INTEGRAL EVALUATION
  (ICUT=11 IN $CONTRL), MORE ACCURATE DIRECT SCF FOCK MATRIX
  CONSTRUCTION (FDIFF=.FALSE. IN $SCF), OR CHANGING THE SCF CONVERGER
  (DIIS=.TRUE. IN $SCF).
  
 Hope this solves the mystery.
  
 Jiabo
 --- On Tue, 5/25/10, Gustavo Mercier gamercier+/-yahoo.com
 <owner-chemistry^^^ccl.net> wrote:
 > From: Gustavo Mercier gamercier+/-yahoo.com
 <owner-chemistry^^^ccl.net>
 Subject: CCL:G: Different single-point DFT energy between GAMESS and Gaussian
 To: "Li, Jiabo " <jiaboli^^^yahoo.com>
 Date: Tuesday, May 25, 2010, 3:32 PM
 Hi!
 In addition to the many suggestions that you have received I would add:
 1. GAMESS direct scf has several short cuts. Look at the control keyword group
 for this. I would get rid of it for both programs.
 2. DIIS also has adjustable parameters, including how much 'history' you keep.
 3. With large basis sets there may be some linear dependencies and the programs
 may automatically make changes in the basis set. Check your output.
 Review the GAMESS documentation and check out the fine print. Look at the file
 "refs.pdf", for example. The developers have made a variety of choices
 in the implementation of different algorithms and they may tell you that their
 choices may result in small differences. However, these can easily be in the
 millihartree or less. You may conclude that getting the exactly the same result
 is not reasonable. This does not even include such details as compiler flags and
 optimization schemes used with different compilers.
  
 --
 Gustavo A. Mercier, Jr., MD, PhD
 gamercier|*|yahoo.com
 Gustavo.Mercier|*|bmc.org
 gumercie|*|bu.edu
 617-414-6440
 > From: Piotr Nowak piotrnowak[*]student.uw.edu.pl
 <owner-chemistry|*|ccl.net>
 To: "Mercier, Gustavo, " <gamercier|*|yahoo.com>
 Sent: Tue, May 25, 2010 1:53:20 PM
 Subject: CCL:G: Different single-point DFT energy between GAMESS and Gaussian
 First of all, thanks everyone for response. Some questions and suggestions
 appeared; I'll try to answer them briefly:
 -I've been using exactly the same structures for the single point energy
 calculations;
 -I have been using spherical harmonics in both programs. Gaussian uses them by
 default, and I have ensured their use in GAMESS with "ISPHER=+1"
 keyword. The number of cartesian basis fuinctions is the same;
 -Gaussian manual states that default grid uses 75 radial shells and 302 angular
 points/shell. I have been using the same grid in GAMESS thanks to
 "NRAD=75" and  "NLEB=302" keywords. I also suspected
 that grid handling might be implemented differently in both programs, therefore
 I tried some "super-ultra-extra-fine" grid with 250 radial shells and
 974 angular points/shell (using "Int(Grid=250974)" keyword in
 Gaussian). Unluckily, the energy difference remained within the same order of
 magnitude as it was with former grid;
 -The relative energies are still different. If you compare e.g. different
 geometries of the same molecule, or activation energies, the error is still
 10^(-4) hartree.
 I would agree with Soren - there must be some "hidden" adjustable
 parameters, but I have no idea which one can cause these differences. I still
 hope it is possible to get the same results using both programs. 
 Kind regards,
 Piotr
 On Tue, May 25, 2010 at 12:50 AM, Piotr Nowak piotrnowak!^!student.uw.edu.pl
 <owner-chemistry]^[ccl.net> wrote:
 Sent to CCL by: "Piotr  Nowak" [piotrnowak~!~student.uw.edu.pl]
 Dear CCL users,
 I'm trying to reproduce single point energy obtained with Gaussian 03 using
 GAMESS US. Hartree-Fock energy is almost exactly the same e.g.
 Gaussian: -1849.26414782
 GAMESS:   -1849.2641478646
 Unfortunately my attempts to get the same results using DFT failed. The
 energy differences between both programs are unreasonably huge. Here are some
 examples of results for different functionals (the same case as above-
 mentioned HF example):
 M05-2X
 Gaussian: -1855.79754118
 GAMESS:   -1855.7976587495
 SVWN5
 Gaussian: -1845.45112047
 GAMESS:   -1845.4510666810
 Slater (also known as Dirac, one of the simplest LDA functionals, so I'm sure
 it has the same definition in both programs)
 Gaussian: -1833.20351470
 GAMESS:   -1833.2034704727
 I have done those calculations using the same grid, using tight convergence
 criteria. I've found out that Gaussian uses slightly different cc-pVDZ basis
 set than the one present in Basis Set Exchange, but using this basis set with
 GAMESS has left the results unchanged. I have also tried different guesses,
 and SCF algorithms, but without success.
 Here are keywords used in inputs for above calculations.
 Gaussian:
 #p m05/cc-pvdz nosymm iop(6/7=3) scf=tight
 GAMESS:
  $BASIS EXTFIL=.TRUE. GBASIS=CCPVDZGN $END
  $CONTRL ISPHER=+1 SCFTYP=RHF RUNTYP=ENERGY DFTTYP=M05 $END
  $SYSTEM PARALL=.TRUE. MWORDS=200 $END
  $SCF DIRSCF=.TRUE. DIIS=.TRUE. $END
  $DFT NRAD=75 NLEB=302 $END
 I would appreciate any kind of help.
 Best regards,
 Piotr Nowak
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 <table cellspacing="0" cellpadding="0"
 border="0" ><tr><td valign="top"
 style="font: inherit;"><DIV>The most likely scenario is the
 basis set linear dependency. GAMESS remove the linear dependent (or more
 precisely, the near linear dependent) component in the basis set space. This
 certainly will slightly change the energies. Here is an example output from
 GAMESS. You can check your log file for similar information:</DIV>
 <DIV>&nbsp;</DIV>
 <DIV><BR>&nbsp;NUMBER OF CARTESIAN ATOMIC
 ORBITALS=&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
 166<BR>&nbsp;NUMBER OF SPHERICAL CONTAMINANTS
 DROPPED=&nbsp;&nbsp;&nbsp;&nbsp; 0<BR>&nbsp;NUMBER OF
 LINEARLY DEPENDENT MOS DROPPED=&nbsp;&nbsp;&nbsp;&nbsp;
 2<BR>&nbsp;TOTAL NUMBER OF MOS IN VARIATION
 SPACE=&nbsp;&nbsp;&nbsp;&nbsp; 164</DIV>
 <DIV>&nbsp;THE INPUT BASIS SET CONTAINS APPROXIMATE LINEAR
 DEPENDENCE.<BR>&nbsp;THE SMALLEST EIGENVALUE OF THE OVERLAP MATRIX
 IS&nbsp;&nbsp; 2.898259E-09<BR>&nbsp;THERE
 ARE&nbsp;&nbsp;&nbsp; 2 EIGENVALUES LESS THAN
 <SPAN>QMTTOL</SPAN>=&nbsp;
 1.00E-07<BR>&nbsp;EIGENVECTORS BELOW -QMTTOL- ARE DROPPED FROM THE MO
 SPACE,<BR>&nbsp;IN ORDER TO ELIMINATE THE APPROXIMATE LINEAR
 DEPENDENCE.</DIV>
 <DIV>&nbsp;THIS WILL MOST LIKELY CHANGE THE ENERGY ON THE ORDER OF
 TENS OF MICROHARTREES,<BR>&nbsp;DEPENDING ON THE NUMBER OF ORBITALS
 REMOVED.&nbsp; THE VALUE OF QMTTOL CAN BE<BR>&nbsp;CHANGED IN
 $CONTRL: JOBS WITH EIGENVALUES BELOW 1.0E-07 PROBABLY
 WON'T<BR>&nbsp;CONVERGE.&nbsp; EIGENVALUES BETWEEN 1.0E-07 AND
 1.0E-06 MAY REQUIRE LOOSENING OF<BR>&nbsp;THE DENSITY CRITERION (CONV
 IN $SCF), MORE ACCURATE INTEGRAL EVALUATION<BR>&nbsp;(ICUT=11 IN
 $CONTRL), MORE ACCURATE DIRECT SCF FOCK MATRIX<BR>&nbsp;CONSTRUCTION
 (FDIFF=.FALSE. IN $SCF), OR CHANGING THE SCF
 CONVERGER<BR>&nbsp;(DIIS=.TRUE. IN $SCF).<BR></DIV>
 <DIV>&nbsp;</DIV>
 <DIV>Hope this solves the mystery.</DIV>
 <DIV>&nbsp;</DIV>
 <DIV>Jiabo<BR><BR>--- On <B>Tue, 5/25/10, Gustavo
 Mercier gamercier+/-yahoo.com
 <I>&lt;owner-chemistry^^^ccl.net&gt;</I></B>
 wrote:<BR></DIV>
 <BLOCKQUOTE style="BORDER-LEFT: rgb(16,16,255) 2px solid; PADDING-LEFT:
 5px; MARGIN-LEFT: 5px"><BR>From: Gustavo Mercier
 gamercier+/-yahoo.com
 &lt;owner-chemistry^^^ccl.net&gt;<BR>Subject: CCL:G: Different
 single-point DFT energy between GAMESS and Gaussian<BR>To: "Li, Jiabo
 " &lt;jiaboli^^^yahoo.com&gt;<BR>Date: Tuesday, May 25, 2010,
 3:32 PM<BR><BR>
 <DIV id=yiv2035807430>
 <STYLE type=text/css><!--#yiv2035807430 DIV
 {margin:0px;}--></STYLE>
 <DIV style="FONT-FAMILY: times new roman, new york, times, serif;
 FONT-SIZE: 12pt">Hi!<BR><BR>In addition to the many
 suggestions that you have received I would add:<BR><BR>1. GAMESS
 direct scf has several short cuts. Look at the control keyword group for this. I
 would get rid of it for both programs.<BR>2. DIIS also has adjustable
 parameters, including how much 'history' you keep.<BR>3. With large basis
 sets there may be some linear dependencies and the programs may automatically
 make changes in the basis set. Check your output.<BR><BR>Review the
 GAMESS documentation and check out the fine print. Look at the file
 "refs.pdf", for example. The developers have made a variety of choices
 in the implementation of different algorithms and they may tell you that their
 choices may result in small differences. However, these can easily be in the
 millihartree or less. You may conclude that getting the exactly the same result
 is not reasonable. This does not even
  include such details as compiler flags and optimization schemes used with
 different compilers.<BR>
 <DIV>&nbsp;</DIV><BR>--<BR>Gustavo A. Mercier, Jr.,
 MD,
 PhD<BR>gamercier|*|yahoo.com<BR>Gustavo.Mercier|*|bmc.org<BR>gumercie|*|bu.edu<BR>617-414-6440<BR><BR>
 <DIV><BR></DIV>
 <DIV style="FONT-FAMILY: times new roman, new york, times, serif;
 FONT-SIZE: 12pt"><BR>
 <DIV style="FONT-FAMILY: times new roman, new york, times, serif;
 FONT-SIZE: 12pt"><FONT size=2 face=Tahoma>
 <HR SIZE=1>
 <B><SPAN style="FONT-WEIGHT:
 bold">From:</SPAN></B> Piotr Nowak
 piotrnowak[*]student.uw.edu.pl
 &lt;owner-chemistry|*|ccl.net&gt;<BR><B><SPAN
 style="FONT-WEIGHT: bold">To:</SPAN></B> "Mercier,
 Gustavo, " &lt;gamercier|*|yahoo.com&gt;<BR><B><SPAN
 style="FONT-WEIGHT: bold">Sent:</SPAN></B> Tue, May 25,
 2010 1:53:20 PM<BR><B><SPAN style="FONT-WEIGHT:
 bold">Subject:</SPAN></B> CCL:G: Different single-point DFT
 energy between GAMESS and Gaussian<BR></FONT><BR>
 <DIV>First of all, thanks everyone for response. Some questions and
 suggestions appeared; I'll try to answer them briefly:</DIV>
 <DIV><BR></DIV>
 <DIV>-I've been using exactly the same structures for the single point
 energy calculations;</DIV>
 <DIV>-I have been using spherical harmonics in both programs. Gaussian
 uses them by default, and I have ensured their use in GAMESS with
 "ISPHER=+1" keyword. The number of cartesian basis fuinctions is the
 same;</DIV>
 <DIV>-Gaussian manual states that default grid uses 75 radial shells and
 302 angular points/shell. I have been using the same grid in GAMESS thanks to
 "NRAD=75" and &nbsp;"NLEB=302" keywords. I also
 suspected that grid handling might be implemented differently in both programs,
 therefore I tried some "super-ultra-extra-fine" grid with 250 radial
 shells and 974 angular points/shell (using "Int(Grid=250974)" keyword
 in Gaussian). Unluckily, the energy difference remained within the same order of
 magnitude as it was with former grid;</DIV>
 <DIV>-The relative energies are still different. If you compare e.g.
 different geometries of the same molecule, or activation energies, the error is
 still 10^(-4) hartree.</DIV>
 <DIV><BR></DIV>
 <DIV>I would agree with Soren - there must be some "hidden"
 adjustable parameters, but I have no idea which one can cause these differences.
 I still hope it is possible to get the same results using both
 programs.&nbsp;</DIV>
 <DIV><BR></DIV>
 <DIV>Kind regards,</DIV>
 <DIV>Piotr</DIV>
 <DIV><BR></DIV><BR>
 <DIV class=gmail_quote>On Tue, May 25, 2010 at 12:50 AM, Piotr Nowak
 piotrnowak!^!<A href="http://student.uw.edu.pl/"; rel=nofollow
 target=_blank>student.uw.edu.pl</A> <SPAN dir=ltr>&lt;<A
 href="http://us.mc369.mail.yahoo.com/mc/compose?to=owner-chemistry]%5E[ccl.net";
 rel=nofollow target=_blank ymailto="mailto:owner-chemistry]%5E[ccl.net";>owner-chemistry]^[ccl.net</A>&gt;</SPAN>
 wrote:<BR>
 <BLOCKQUOTE style="BORDER-LEFT: rgb(204,204,204) 1px solid; MARGIN: 0pt
 0pt 0pt 0.8ex; PADDING-LEFT: 1ex" class=gmail_quote><BR>Sent to
 CCL by: "Piotr &nbsp;Nowak" [piotrnowak~!~<A href="http://student.uw.edu.pl/"; rel=nofollow
 target=_blank>student.uw.edu.pl</A>]<BR>Dear CCL
 users,<BR><BR>I'm trying to reproduce single point energy obtained
 with Gaussian 03 using<BR>GAMESS US. Hartree-Fock energy is almost exactly
 the same e.g.<BR>Gaussian: -1849.26414782<BR>GAMESS: &nbsp;
 -1849.2641478646<BR><BR>Unfortunately my attempts to get the same
 results using DFT failed. The<BR>energy differences between both programs
 are unreasonably huge. Here are some<BR>examples of results for different
 functionals (the same case as above-<BR>mentioned HF
 example):<BR>M05-2X<BR>Gaussian: -1855.79754118<BR>GAMESS:
 &nbsp; -1855.7976587495<BR>SVWN5<BR>Gaussian:
 -1845.45112047<BR>GAMESS: &nbsp; -1845.4510666810<BR>Slater
 (also known as Dirac, one of the simplest LDA functionals,
  so I'm sure<BR>it has the same definition in both
 programs)<BR>Gaussian: -1833.20351470<BR>GAMESS: &nbsp;
 -1833.2034704727<BR><BR>I have done those calculations using the
 same grid, using tight convergence<BR>criteria. I've found out that
 Gaussian uses slightly different cc-pVDZ basis<BR>set than the one present
 in Basis Set Exchange, but using this basis set with<BR>GAMESS has left
 the results unchanged. I have also tried different guesses,<BR>and SCF
 algorithms, but without success.<BR><BR>Here are keywords used in
 inputs for above calculations.<BR>Gaussian:<BR>#p m05/cc-pvdz nosymm
 iop(6/7=3) scf=tight<BR><BR>GAMESS:<BR>&nbsp;$BASIS
 EXTFIL=.TRUE. GBASIS=CCPVDZGN $END<BR>&nbsp;$CONTRL ISPHER=+1
 SCFTYP=RHF RUNTYP=ENERGY DFTTYP=M05 $END<BR>&nbsp;$SYSTEM
 PARALL=.TRUE. MWORDS=200 $END<BR>&nbsp;$SCF DIRSCF=.TRUE. DIIS=.TRUE.
 $END<BR>&nbsp;$DFT NRAD=75 NLEB=302 $END<BR><BR>I would
 appreciate any kind of help.<BR>Best regards,<BR>Piotr
  Nowak<BR><BR><BR><BR><BR>E-mail to subscribers:
 <A href="http://us.mc369.mail.yahoo.com/mc/compose?to=CHEMISTRY]%5E[ccl.net";
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