CCL:G: Different single-point DFT energy between GAMESS and Gaussian
- From: Brian Salter-Duke <brian.james.duke : gmail.com>
- Subject: CCL:G: Different single-point DFT energy between GAMESS
and Gaussian
- Date: Wed, 26 May 2010 19:52:30 +0100
Sent to CCL by: Brian Salter-Duke [brian.james.duke::gmail.com]
Have you asked Mike Schmidt of GAMESS(US) whether the GAMESS results
should be identical to Gaussian?
On Wed, May 26, 2010 at 04:54:12PM +0200, Piotr Nowak
piotrnowak*o*student.uw.edu.pl wrote:
> Several new plausible solutions to the problems have been made. Because the
> problem has been more difficult than I had thought, I've checked those
> suggestions on a simpler test case, namely: 1-fluoroethanol, using the
> geometry below:
>
> C 6 -1.371551 -0.189402 -0.078069
> C 6 0.055735 -0.002315 0.345325
> H 1 -1.765264 -1.132234 0.321003
> H 1 -1.422818 -0.219081 -1.174187
> H 1 -1.987781 0.640525 0.287358
> O 8 0.815913 -1.025112 -0.171888
> H 1 0.154695 0.068673 1.446323
> F 9 0.519096 1.212587 -0.140203
> H 1 1.716903 -0.919975 0.152892
>
> - Christopher Cramer suggested that different spatial orientation may cause
> different results. The "nosymm" Gaussian keyword indeed suppreses
any
> orientation changes, so input orientation is used throughout the
> calculations. GAMESS doesn't change the orientation by default, so
> calculations performed using "nosymm" are made on the same
geometry. I was
> curious if changing the initial orientation (called "InitOr in the
table
> below - different than the orientation above) to the standard one, can
> change the results significantly. If "nosymm" is not present,
Gaussian
> rotates the molecule to the standard orientation (StdOr). In order to do
the
> same using GAMESS, "COORD=PRINAXIS" keyword is required. I've
found out that
> when using standard orientation from the Gaussian output and pasting it to
> the GAMESS input (now without "coord=prinaxis), GAMESS gives different
> result than by rotating the molecule to the principal axis by itself!
> Therefore in all subsequent GAMESS calculations I was using standard
> orientation from Gaussian output (the one above). The results are presented
> below (using M05/cc-pVDZ and grid(75,302)), together with HF energies,
which
> are pretty much reproducible, and M05 calculations using much better than
> standard grid (250,974):
>
> Gaussian:
> -254.175261128 (InitOr,nosymm)
> -254.175313014 (StdOr transformed from InitOr by Gaussian)
> GAMESS:
> -254.1753800399 (InitOr)
> -254.1753738096 (InitOr with "COORD=PRINAXIS" keyword)
> -254.1753375023 (StdOr)
> Grid(250,974):
> -254.175301121 (Gaussian, StdOr)
> -254.1753365149 (GAMESS, InitOr, "PRINAXIS")
> -254.1753372591 (GAMESS, StdOr)
> Hartree-Fock:
> -252.967151367 (Gaussian)
> -252.9671513780 (GAMESS)
>
> - Many people said that linear dependencies could be the cause. That's very
> unlikely with cc-pVDZ, and there are no linearly dependent MOs present in
my
> GAMESS outputs.
> - The symmetry is C1 in all cases.
> - There are no transition metals present.
> - I know that GAMESS interprets CCD keyword as cc-pV(D+d)Z basis set
instead
> of cc-pVDZ. That's why I was using explicitely defined cc-pVDZ atomic basis
> set in GAMESS, exactly the one used by Gaussian ("gfinput"
switches on
> printing of basis set info in Gaussian).
> - Another source of error is grid pruning in Gaussian. To avoid this, grid
> should be requested using e.g. "int(grid=75302)" instead of
> "int(grid=finegrid)". There are two weighing schemes available in
Gaussian.
> The scheme of Scuseria and Stratman ("ssweights) is the default, and
Becke
> scheme can be requested using "bweights". I don't have any ideas
how
> weighing is performed by GAMESS. Unfortunatly changing those options still
> does not give similar results:
> -254.175313014 (Gaussian - int(grid=finegrid), ssweights)
> -254.175298048 (Gaussian - int(grid=75302), ssweights)
> -254.175297910 (Gaussian - int(grid=75302), bweights)
> -254.1753375023 (GAMESS)
>
> I'm afraid hat the whole idea of reproducibility of results is going to
fail
> in case of DFT, but I still hope that it can see the light in the darkness.
> Somwhere...
>
> Best Regards,
> Piotr
>
> On Tue, May 25, 2010 at 7:53 PM, Piotr Nowak piotrnowak[*]student.uw.edu.pl
> <owner-chemistry(!)ccl.net> wrote:
>
> > 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<owner-chemistry]%5E%5Bccl.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>> E-mail to subscribers: CHEMISTRY]^[ccl.net
<CHEMISTRY]%5E%5Bccl.net> or
> >> use:>>
> >> E-mail to administrators:
CHEMISTRY-REQUEST]^[ccl.net<CHEMISTRY-REQUEST]%5E%5Bccl.net>or use>>
> >>
> >>
> >
> >
>
>
> --
> http://www.slayer.net/us/orderwpb
--
Brian Salter-Duke (Brian Duke)
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