Subject: Gaussian98 + symmetry + elec. states

From: B Barnes <[email-masked]>
Date: Wed, 7 May 2003 13:16:46 -0500 (CDT)

Hello all,

I'm a longtime reader and infrequent poster to the list.  I've encountered
a very curious problem recently with gaussian98, attempting to do a MP2
single-point energy calculation on a benezenethiolate-gold molecule,
C6H5SAu, with Cs symmetry.  The basis set is cc-pVDZ for C/H/S and
Stuttgart RSC 1997 ECP for Au (from the EMSL Gaussian Basis Set Library).

Depending upon whether or not I enable use of symmetry, I get
significantly different results (absolute electronic energies differ by
about 100 kcal/mol). In fact, if you inspect the MO's produced, it appears
the calc. actually converges to different electronic states.

Lastly, this odd result is not unique to g98 -- when doing the calculation
with NWChem, I also get different results depending on whether symmetry is
enabled, but the reverse of g98: the result for g98 with symmetry is the
same as NWChem without symmetry, and vice-versa!  I contacted NWChem
users/developers in a different forum; I expect CCL will be more familiar
with Gaussian.

So my questions are... what exactly is going on?  How can I fix this
problem so that I know the calculation is being done properly for the
ground state?

Attached below it my input file -- simply remove 'NoSymm' and you have my
input file for the calc. without symmetry.  If anyone is interested, I can
also provide output.

Thanks,

Brian Barnes

#P RMP2(RW )/GEN 5D Pseudo(Read) NoSymm  Punch=(MO) Density Pop=(Full)

benz_Au_geom_Cs_3_g98_ws

0 1 ! charge and multiplicity
 C     1.58336     3.55548     0.00000
 H     1.58140     4.64991     0.00000
 C     1.58431     2.84386     1.21149
 H     1.58086     3.38176     2.16605
 C     1.58431     1.43882     1.21987
 H     1.59499     0.894548     2.17036
 C     1.58653     0.718905     0.00000
 C     1.58431     1.43882     -1.21987
 H     1.59499     0.894548     -2.17036
 C     1.58431     2.84386     -1.21149
 H     1.58086     3.38176     -2.16605
 S     1.55967     -1.04500     0.00000
 Au     -1.13836     -0.930645     0.00000

 H  0
 S   3  1.00
      13.01000000      0.01968500
       1.96200000      0.13797700
       0.44460000      0.47814800
 S   1  1.00
       0.12200000      1.00000000
 P   1  1.00
       0.72700000      1.00000000
 ****
 S  0
 S  11  1.00
  110800.00000000      0.00024800
   16610.00000000      0.00192000
    3781.00000000      0.00996200
    1071.00000000      0.04029700
     349.80000000      0.12860400
     126.30000000      0.30348000
      49.26000000      0.42143200
      20.16000000      0.23078100
       5.72000000      0.01789700
       2.18200000     -0.00297500
       0.43270000      0.00085000
 S  11  1.00
  110800.00000000     -0.00006900
   16610.00000000     -0.00052800
    3781.00000000     -0.00279700
    1071.00000000     -0.01126500
     349.80000000     -0.03888300
     126.30000000     -0.09950200
      49.26000000     -0.19974000
      20.16000000     -0.12336000
       5.72000000      0.51319400
       2.18200000      0.60712000
       0.43270000      0.03967500
 S  11  1.00
  110800.00000000      0.00002000
   16610.00000000      0.00015300
    3781.00000000      0.00081000
    1071.00000000      0.00329000
     349.80000000      0.01129700
     126.30000000      0.02963900
      49.26000000      0.05998500
      20.16000000      0.04132500
       5.72000000     -0.20747400
       2.18200000     -0.39288900
       0.43270000      0.63284000
 S   1  1.00
       0.15700000      1.00000000
 P   7  1.00
     399.70000000      0.00447500
      94.19000000      0.03417100
      29.75000000      0.14425000
      10.77000000      0.35392800
       4.11900000      0.45908500
       1.62500000      0.20638300
       0.47260000      0.01021400
 P   7  1.00
     399.70000000     -0.00116300
      94.19000000     -0.00865700
      29.75000000     -0.03908900
      10.77000000     -0.09346300
       4.11900000     -0.14799400
       1.62500000      0.03019000
       0.47260000      0.56157300
 P   1  1.00
       0.14070000      1.00000000
 D   1  1.00
       0.47900000      1.00000000
 ****
 AU  0
 S   2  1.00
      30.19653700      0.00473300
       9.72597300     -0.35438200
 S   1  1.00
       5.08040600      1.00000000
 S   1  1.00
       1.72265700      1.00000000
 S   1  1.00
       0.72645900      1.00000000
 S   1  1.00
       0.09035400      1.00000000
 S   1  1.00
       0.02210600      1.00000000
 S   1  1.00
       0.00641500      1.00000000
 P   4  1.00
      13.83821900      0.03617900
       5.19578700     -0.32830300
       1.79804500      0.66538800
       0.66610500      0.55266600
 P   1  1.00
       0.15433600      1.00000000
 P   1  1.00
       0.03400000      1.00000000
 D   2  1.00
       6.33700100     -0.04410300
       1.48069700      0.46211500
 D   1  1.00
       0.52838200      1.00000000
 D   1  1.00
       0.17111700      1.00000000
 D   1  1.00
       0.04551200      1.00000000
 ****
 C  0
 S   8  1.00
    6665.00000000      0.00069200
    1000.00000000      0.00532900
     228.00000000      0.02707700
      64.71000000      0.10171800
      21.06000000      0.27474000
       7.49500000      0.44856400
       2.79700000      0.28507400
       0.52150000      0.01520400
 S   8  1.00
    6665.00000000     -0.00014600
    1000.00000000     -0.00115400
     228.00000000     -0.00572500
      64.71000000     -0.02331200
      21.06000000     -0.06395500
       7.49500000     -0.14998100
       2.79700000     -0.12726200
       0.52150000      0.54452900
 S   1  1.00
       0.15960000      1.00000000
 P   3  1.00
       9.43900000      0.03810900
       2.00200000      0.20948000
       0.54560000      0.50855700
 P   1  1.00
       0.15170000      1.00000000
 D   1  1.00
       0.55000000      1.00000000
 ****

AU  0
AU-ECP   4   60
g potential
 1
2        1.00000000      0.00000000
s-g potential
 2
2       13.20510000    426.70984000
2        6.60255000     35.93882400
p-g potential
 2
2       10.45202000    261.16102300
2        5.22601000     26.62628400
d-g potential
 2
2        7.85110000    124.75683100
2        3.92555000     15.77226000
f-g potential
 2
2        4.78980000     30.56847500
2        2.39491000      5.18377400

9,0