CCL:G: FW: G: Different single-point DFT energy between GAMESS and Gaussian
- From: "Rinderspacher, Berend (Cont, ARL/WMRD)"
- Subject: CCL:G: FW: G: Different single-point DFT energy between
GAMESS and Gaussian (UNCLASSIFIED)
- Date: Wed, 26 May 2010 15:42:36 -0400
Sent to CCL by: "Rinderspacher, Berend (Cont, ARL/WMRD)"
The errors between Gaussian and Gamess are on the same level as the
errors within Gaussian or Gamess, ~10^-4 a.u. Unless you believe that
M05 produces subchemical accuracy these results are the same for all
chemical intents and purposes. Also M05 contains a slew of parameters.
Do you find the same discrepancies with "simpler" functionals (BLYP,
B3LYP, PBE, PBE0)?
Subject: CCL:G: Different single-point DFT energy between GAMESS and
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
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
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
-254.175313014 (StdOr transformed from InitOr by Gaussian)
-254.1753738096 (InitOr with "COORD=PRINAXIS" keyword)
-254.175301121 (Gaussian, StdOr)
-254.1753365149 (GAMESS, InitOr, "PRINAXIS")
-254.1753372591 (GAMESS, StdOr)
- 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
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)
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
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
-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
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
On Tue, May 25, 2010 at 12:50 AM, Piotr Nowak
<blockedmailto:owner-chemistry]%5E%5Bccl.net> > wrote:
Sent to CCL by: "Piotr Nowak"
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
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):
Slater (also known as Dirac, one of the simplest LDA
functionals, so I'm sure
it has the same definition in both programs)
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
and SCF algorithms, but without success.
Here are keywords used in inputs for above calculations.
#p m05/cc-pvdz nosymm iop(6/7=3) scf=tight
$BASIS EXTFIL=.TRUE. GBASIS=CCPVDZGN $END
$CONTRL ISPHER=+1 SCFTYP=RHF RUNTYP=ENERGY DFTTYP=M05
$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.
-= This is automatically added to each message by the
mailing script =-
E-mail to subscribers: CHEMISTRY]^[ccl.net
<blockedmailto:CHEMISTRY]%5E%5Bccl.net> or use:<blockedhttp://www.ccl.net/cgi-bin/ccl/send_ccl_message>
E-mail to administrators: CHEMISTRY-REQUEST]^[ccl.net