Subject: Virial theorem: -V/T=10.2 in Gaussian 94 !

From: shochen michael <[email-masked]>
Date: Tue, 17 Jun 1997 12:16:44 +0300 (IDT)

Dear users of the Gaussian 94,

 Gaussian 94, Revision D.1 is in a serious conflict with 
the Virial theorem ( -V/T = 2 ): the calculated values are 
10.1875 for the RHF/6-31+G* , and
12.8451 for the RHF/D95+(d) 

What is very funny, that in all of the cases I got a message 
>from Gaussian about the normal termination!
  These strange results I got for different molecules.
I think that something is wrong with the diffusion basis 
sets (+), because the calculations of the same molecules 
performed in the  RHF/6-31* or B3LYP/6-31*  satisfied to
the Virial theorem. In addition. In some of my calculations,
where RHF/6-31+G* gave the correct results, the B3LYP/6-31+G*
failed in the middle of calculation. In contrary, the 
B3LYP/6-31* gave the correct results with the normal termination.
 The problem is that I need to calculate anionic systems,
so I need to use the basis sets containing the diffusion 
functions. I'll be very appreciated if somebody give me an 
advice how to work aroud.

Thank you in advance,
Michael

P.S. Please find enclosed one example, where the Gaussian 94 
failed in the Viral theorem, but gave a message about
the normal termination. The first is an input file,
which is followed by the fragments of the related output file. 

*******************************************

%Chk=ts3
%Mem=10000000
# RHF/6-31+G* SCF=DIRECT TEST

 TC ANION 3-21G* OPTIMIZED

  -1   1
 C
 C,1,R2
 C,1,R3,2,A3
 C,1,R4,2,A4,3,D4,0
 C,2,R5,1,A5,3,D5,0
 C,3,R6,1,A6,2,D6,0
 C,4,R7,1,A7,2,D7,0
 O,4,R8,1,A8,7,D8,0
 O,2,R9,1,A9,5,D9,0
 O,3,R10,1,A10,6,D10,0
 S,4,R11,1,A11,7,D11,0
 C,5,R12,2,A12,1,D12,0
 Cl,5,R13,2,A13,12,D13,0
 Cl,6,R14,3,A14,1,D14,0
 H,7,R15,4,A15,1,D15,0
 H,7,R16,4,A16,15,D16,0
 H,7,R17,4,A17,15,D17,0
 H,8,R18,4,A18,1,D18,0
 C,11,R19,4,A19,1,D19,0
 H,10,R20,3,A20,1,D20,0
 H,12,R21,5,A21,2,D21,0
 H,19,R22,11,A22,4,D22,0
 H,19,R23,11,A23,22,D23,0
 H,19,R24,11,A24,22,D24,0
      Variables:
 R2=1.433
 R3=1.38673862
 R4=1.5390065
 R5=1.41828911
 R6=1.3844898
 R7=1.53794766
 R8=1.41649921
 R9=1.28195164
 R10=1.3775275
 R11=1.87361576
 R12=1.36318964
 R13=1.75653209
 R14=1.7541639
 R15=1.08280284
 R16=1.08309972
 R17=1.07916032
 R18=1.01268356
 R19=1.80866221
 R20=0.97133208
 R21=1.06989205
 R22=1.07949525
 R23=1.08005278
 R24=1.08174442
 A3=120.89289857
 A4=118.78207179
 A5=115.11617584
 A6=120.72497989
 A7=110.9080782
 A8=113.1871631
 A9=123.41661447
 A10=122.47355805
 A11=111.8749713
 A12=123.44545454
 A13=117.47214039
 A14=120.32194677
 A15=109.33924187
 A16=107.18210973
 A17=111.48826877
 A18=108.39740524
 A19=97.79784087
 A20=111.00502497
 A21=120.27528426
 A22=106.25519656
 A23=111.30530935
 A24=108.92560816
 D4=-176.2593885
 D5=0.98160734
 D6=-0.86658381
 D7=115.23042257
 D8=-121.8826806
 D9=179.44676434
 D10=-179.28132269
 D11=119.13311047
 D12=-0.29849994
 D13=179.82921589
 D14=179.51507708
 D15=179.93467218
 D16=117.73509895
 D17=-122.73099561
 D18=6.33840667
 D19=66.14258581
 D20=-39.70418622
 D21=-179.97219346
 D22=44.76253312
 D23=-119.69422493
 D24=118.82376558
******************************************

 Entering Gaussian System, Link 0=g94
 Initial command:
 /ext/g94/l1.exe /tmp/g94-8024.inp -scrdir=/tmp/
 Entering Link 1 = /ext/g94/l1.exe PID=      8026.
  
 Cite this work as:
 Gaussian 94, Revision D.1,
 M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill,
 B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith,
 G. A. Petersson, J. A. Montgomery, K. Raghavachari,
 M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman,
 J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe,
 C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres,
 E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox,
 J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart,
 M. Head-Gordon, C. Gonzalez, and J. A. Pople,
 Gaussian, Inc., Pittsburgh PA, 1995.
  
 ***************************************
 Gaussian 94:  SGI-G94RevD.1  1-Feb-1996
               26-May-1997
 ***************************************
 %Chk=ts3
 %Mem=10000000
 -----------------------------
 # RHF/6-31+G* SCF=DIRECT TEST
 -----------------------------
 1/38=1/1;
 2/12=2,17=6,18=5/2;
 3/5=1,6=6,7=11,11=1,25=1,30=1/1,2,3;
 4/7=1/1;
 5/5=2,32=1,38=4/2;
 6/7=2,8=2,9=2,10=2,19=1,28=1/1;
 99/5=1,9=1/99;
 -------------------------
 TC ANION 3-21G* OPTIMIZED
 -------------------------
 Symbolic Z-matrix:
    Charge =-1 Multiplicity = 1
 C
 C     1     R2
 C     1     R3        2     A3
 C     1     R4        2     A4        3     D4        0
 C     2     R5        1     A5        3     D5        0
 C     3     R6        1     A6        2     D6        0
 C     4     R7        1     A7        2     D7        0
 O     4     R8        1     A8        7     D8        0
 O     2     R9        1     A9        5     D9        0
 O     3     R10       1     A10       6     D10       0
 S     4     R11       1     A11       7     D11       0
 C     5     R12       2     A12       1     D12       0
 Cl    5     R13       2     A13       12    D13       0
 Cl    6     R14       3     A14       1     D14       0
 H     7     R15       4     A15       1     D15       0
 H     7     R16       4     A16       15    D16       0
 H     7     R17       4     A17       15    D17       0
 H     8     R18       4     A18       1     D18       0
 C     11    R19       4     A19       1     D19       0
 H     10    R20       3     A20       1     D20       0
 H     12    R21       5     A21       2     D21       0
 H     19    R22       11    A22       4     D22       0
 H     19    R23       11    A23       22    D23       0
 H     19    R24       11    A24       22    D24       0
       Variables:
  R2                    1.433                    
  R3                    1.38674                  
  R4                    1.53901                  
  R5                    1.41829                  
  R6                    1.38449                  
  R7                    1.53795                  
  R8                    1.4165                   
  R9                    1.28195                  
  R10                   1.37753                  
  R11                   1.87362                  
  R12                   1.36319                  
  R13                   1.75653                  
  R14                   1.75416                  
  R15                   1.0828                   
  R16                   1.0831                   
  R17                   1.07916                  
  R18                   1.01268                  
  R19                   1.80866                  
  R20                   0.97133                  
  R21                   1.06989                  
  R22                   1.0795                   
  R23                   1.08005                  
  R24                   1.08174                  
  A3                  120.8929                   
  A4                  118.78207                  
  A5                  115.11618                  
  A6                  120.72498                  
  A7                  110.90808                  
  A8                  113.18716                  
  A9                  123.41661                  
  A10                 122.47356                  
  A11                 111.87497                  
  A12                 123.44545                  
  A13                 117.47214                  
  A14                 120.32195                  
  A15                 109.33924                  
  A16                 107.18211                  
  A17                 111.48827                  
  A18                 108.39741                  
  A19                  97.79784                  
  A20                 111.00502                  
  A21                 120.27528                  
  A22                 106.2552                   
  A23                 111.30531                  
  A24                 108.92561                  
  D4                 -176.25939                  
  D5                    0.98161                  
  D6                   -0.86658                  
  D7                  115.23042                  
  D8                 -121.88268                  
  D9                  179.44676                  
  D10                -179.28132                  
  D11                 119.13311                  
  D12                  -0.2985                   
  D13                 179.82922                  
  D14                 179.51508                  
  D15                 179.93467                  
  D16                 117.7351                   
  D17                -122.731                    
  D18                   6.33841                  
  D19                  66.14259                  
  D20                 -39.70419                  
  D21                -179.97219                  
  D22                  44.76253                  
  D23                -119.69422                  
  D24                 118.82377                  
 
Rotational constants (GHZ):      0.5087519      0.3695608      0.2482086
 Isotopes: C-12,C-12,C-12,C-12,C-12,C-12,C-12,O-16,O-16,O-16,S-32,C-12,Cl-35,Cl-3
 5,H-1,H-1,H-1,H-1,C-12,H-1,H-1,H-1,H-1,H-1
 Standard basis: 6-31+G(d) (6D, 7F)
 There are   315 symmetry adapted basis functions of A   symmetry.
 Crude estimate of integral set expansion from redundant integrals=1.000.
 Integral buffers will be    262144 words long.
 Raffenetti 1 integral format.
 Two-electron integral symmetry is turned on.
   315 basis functions      588 primitive gaussians
    69 alpha electrons       69 beta electrons
       nuclear repulsion energy      1398.0344976685 Hartrees.
 One-electron integrals computed using PRISM.
 There are   5 eigenvalues of the overlap less than 1.0D-05
 The smallest eigenvalue of the overlap matrix is  9.126D-07
 Projected CNDO Guess.
 Warning!  Cutoffs for single-point calculations used.
 Requested convergence on RMS density matrix=1.00D-04 within  64 cycles.
 Requested convergence on MAX density matrix=1.00D-02.
 Requested convergence on             energy=5.00D-05.
 Restarting both DIIS and incremental Fock formation.
 Restarting both DIIS and incremental Fock formation.
 Convergence on energy, delta-E=3.33D-05
 SCF Done:  E(RHF) =  -17398.0240946     A.U. after   45 cycles
             Convg  =    0.2007D-03             -V/T = 10.1875
             S**2   =   0.0000

 **********************************************************************

            Population analysis using the SCF density.

 **********************************************************************

 Alpha  occ. eigenvalues -- ********************-396.43580-185.98863-106.54088
 Alpha  occ. eigenvalues -- -106.43078 -93.41316 -35.15903 -25.79301 -22.01826
 Alpha  occ. eigenvalues --  -21.87731 -21.82000 -12.58010 -12.55300 -12.53076
 Alpha  occ. eigenvalues --  -12.49788 -12.46177 -12.44858 -12.42837 -12.41377

 N-N= 1.398034497668D+03 E-N=-7.089851088751D+03  KE= 1.893656502354D+03

 Test job not archived.
 1\1\GINC-ETGAR\SP\RHF\6-31+G(d)\C9H9Cl2O3S1(1-)\SHOKHEN\26-May-1997\0\
 \# RHF/6-31+G* SCF=DIRECT TEST\\TC ANION 3-21G* OPTIMIZED\\-1,1\C\C,1,
 1.433\C,1,1.38673862,2,120.89289857\C,1,1.5390065,2,118.78207179,3,-17
 6.2593885,0\C,2,1.41828911,1,115.11617584,3,0.98160734,0\C,3,1.3844898
 ,1,120.72497989,2,-0.86658381,0\C,4,1.53794766,1,110.9080782,2,115.230
 42257,0\O,4,1.41649921,1,113.1871631,7,-121.8826806,0\O,2,1.28195164,1
 ,123.41661447,5,179.44676434,0\O,3,1.3775275,1,122.47355805,6,-179.281
 32269,0\S,4,1.87361576,1,111.8749713,7,119.13311047,0\C,5,1.36318964,2
 ,123.44545454,1,-0.29849994,0\Cl,5,1.75653209,2,117.47214039,12,179.82
 921589,0\Cl,6,1.7541639,3,120.32194677,1,179.51507708,0\H,7,1.08280284
 ,4,109.33924187,1,179.93467218,0\H,7,1.08309972,4,107.18210973,15,117.
 73509895,0\H,7,1.07916032,4,111.48826877,15,-122.73099561,0\H,8,1.0126
 8356,4,108.39740524,1,6.33840667,0\C,11,1.80866221,4,97.79784087,1,66.
 14258581,0\H,10,0.97133208,3,111.00502497,1,-39.70418622,0\H,12,1.0698
 9205,5,120.27528426,2,-179.97219346,0\H,19,1.07949525,11,106.25519656,
 4,44.76253312,0\H,19,1.08005278,11,111.30530935,22,-119.69422493,0\H,1
 9,1.08174442,11,108.92560816,22,118.82376558,0\\Version=SGI-G94RevD.1\
 HF=-17398.0240946\RMSD=2.007e-04\Dipole=9.4475259,-10.235066,-23.44202
 57\PG=C01 [X(C9H9Cl2O3S1)]\\@

 SCIENCE AND PEACE WILL TRIUMPH OVER IGNORANCE AND WAR

                          -- PASTEUR
 Job cpu time:  0 days  9 hours 12 minutes  7.4 seconds.
 File lengths (MBytes):  RWF=   85 Int=    0 D2E=    0 Chk=    6 Scr=    1
 Normal termination of Gaussian 94

*********************************************************

Dr. Michael Shokhen
Senior researcher,
Department of Biochemistry,
G.S.Wise Faculty of Life Sciences,
Tel-Aviv University,
69978, Tel-Aviv, Israel.
Fax: 972-3-6415053
Email: [email-masked]

*********************************************************