57/5000 I work transition metals dimer. psi4 missing the number of electrons

Hi , I’m working transition metals dimer such as (Fe2,Cu2,Ag2,Au2,) on psi4.

SCF program
It’s missing the number of electrons.It must be 94 electron for Ag2.But scf program show 38 electron.
For 3d transition metals program working properly. But psi4 can not working properly 4d,5d transition metal.
Here is my input

molecule mol{
0 1
Ag
Ag 1 R
#symmetry c1
}

set {
basis def2-qzvpp
df_basis_scf def2-qzvpp-jkfit
df_basis_cc def2-qzvpp-ri
scf_type df
reference rohf
guess sad
soscf true
maxiter 50000
compute_s2 true
}

And here is my output

==> Geometry <==

Molecular point group: d2h
Full point group: D_inf_h

Geometry (in Angstrom), charge = 0, multiplicity = 1:

   Center              X                  Y                   Z               Mass       
------------   -----------------  -----------------  -----------------  -----------------
      AG          0.000000000000     0.000000000000    -0.600000000000   106.905096820000
      AG          0.000000000000     0.000000000000     0.600000000000   106.905096820000

Running in d2h symmetry.

Rotational constants: A = ************ B = 0.21901 C = 0.21901 [cm^-1]
Rotational constants: A = ************ B = 6565.77942 C = 6565.77942 [MHz]
Nuclear repulsion = 159.194143584158297

Charge = 0
Multiplicity = 1
Electrons = 38
Nalpha = 19
Nbeta = 19

==> Algorithm <==

SCF Algorithm Type is DF.
DIIS enabled.
MOM disabled.
Fractional occupation disabled.
Guess Type is SAD.
Energy threshold = 1.00e-08
Density threshold = 1.00e-08
Integral threshold = 0.00e+00

==> Primary Basis <==

Basis Set: DEF2-QZVPP
Blend: DEF2-QZVPP
Number of shells: 44
Number of basis function: 176
Number of Cartesian functions: 232
Spherical Harmonics?: true
Max angular momentum: 4

Core potential: DEF2-QZVPP
Number of shells: 8
Number of ECP primitives: 28
Number of ECP core electrons: 56
Max angular momentum: 3

=> Loading Basis Set <=

Name: DEF2-QZVPP-JKFIT
Role: JKFIT
Keyword: DF_BASIS_SCF
atoms 1-2 entry AG         line  4372 file /usr/local/programs/psi4intel/share/psi4/basis/def2-qzvpp-jkfit.gbs 

==> Pre-Iterations <==


Irrep   Nso     Nmo     Nalpha   Nbeta   Ndocc  Nsocc

 Ag        34      34       0       0       0       0
 B1g       12      12       0       0       0       0
 B2g       21      21       0       0       0       0
 B3g       21      21       0       0       0       0
 Au        12      12       0       0       0       0
 B1u       34      34       0       0       0       0
 B2u       21      21       0       0       0       0
 B3u       21      21       0       0       0       0

Total     176     176      19      19      19       0

==> Integral Setup <==

==> DFJK: Density-Fitted J/K Matrices <==

J tasked:                  Yes
K tasked:                  Yes
wK tasked:                  No
OpenMP threads:              8
Integrals threads:           8
Memory (MB):              1430
Algorithm:                Core
Integral Cache:           NONE
Schwarz Cutoff:          1E-12
Fitting Condition:       1E-12

=> Auxiliary Basis Set <=

Basis Set: DEF2-QZVPP-JKFIT
Blend: DEF2-QZVPP-JKFIT
Number of shells: 98
Number of basis function: 510
Number of Cartesian functions: 768
Spherical Harmonics?: true
Max angular momentum: 6

Minimum eigenvalue in the overlap matrix is 6.4033864309E-05.
Using Symmetric Orthogonalization.

SCF Guess: Superposition of Atomic Densities via on-the-fly atomic UHF.

==> Iterations <==

                       Total Energy        Delta E     RMS |[F,P]|

@DF-ROHF iter 0: 384.84701785348722 3.84847e+02 0.00000e+00
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 5, 1, 2, 2, 1, 4, 2, 2 ]
SOCC [ 0, 0, 0, 0, 0, 0, 0, 0 ]

@DF-ROHF iter 1: 137.67835210954050 -2.47169e+02 1.87957e-01
@DF-ROHF iter 2: -268.32970246156310 -4.06008e+02 1.93738e-01 DIIS
@DF-ROHF iter 3: -284.43489721042863 -1.61052e+01 7.49294e-02 DIIS
@DF-ROHF iter 4: -287.80721837490921 -3.37232e+00 3.14589e-02 DIIS
@DF-ROHF iter 5: -288.27900254953454 -4.71784e-01 5.81245e-03 DIIS
@DF-ROHF iter 6: -288.31433817694779 -3.53356e-02 2.09626e-03 SOSCF, nmicro = 5
@DF-ROHF iter 7: -288.32384078990253 -9.50261e-03 1.57571e-04 SOSCF, nmicro = 5
@DF-ROHF iter 8: -288.32390325668325 -6.24668e-05 2.15838e-06 SOSCF, nmicro = 5
@DF-ROHF iter 9: -288.32390326088080 -4.19755e-09 1.16808e-08 SOSCF, nmicro = 5
@DF-ROHF iter 10: -288.32390326088102 -2.27374e-13 5.90623e-11 SOSCF, nmicro = conv

==> Post-Iterations <==

Orbital Energies (a.u.)
-----------------------

Doubly Occupied:                                                      

   1Ag    -5.365556     1B1u   -4.560842     2Ag    -3.736081  
   1B3u   -3.428944     1B2u   -3.428944     1B2g   -3.053256  
   1B3g   -3.053256     2B1u   -2.636671     2B2u   -1.340746  
   2B3u   -1.340746     3Ag    -1.198718     1B1g   -1.055562  
   4Ag    -1.055562     1Au    -0.704581     3B1u   -0.704581  
   2B3g   -0.431967     2B2g   -0.431967     5Ag    -0.365714  
   4B1u   -0.236355  

Singly Occupied:                                                      



Virtual:                                                              

   3B3u   -0.026592     3B2u   -0.026592     5B1u    0.047330  
   6Ag     0.058131     3B2g    0.066150     3B3g    0.066150  
   4B3u    0.075899     4B2u    0.075899     7Ag     0.089244  
   6B1u    0.150563     8Ag     0.179600     4B3g    0.194702  
   4B2g    0.194702     7B1u    0.198018     2B1g    0.273375  
   9Ag     0.273375     8B1u    0.343739     5B3u    0.372868  
   5B2u    0.372868     9B1u    0.394969     2Au     0.394969  
  10Ag     0.427898    11Ag     0.449245     5B2g    0.476070  
   5B3g    0.476070    10B1u    0.478861     6B3u    0.485602  
   6B2u    0.485602     7B2u    0.505033     7B3u    0.505033  
   6B2g    0.650003     6B3g    0.650003    12Ag     0.658249  
   3B1g    0.669839    13Ag     0.669839     7B2g    0.704438  
   7B3g    0.704438    11B1u    0.778722    12B1u    0.870861  
   3Au     0.870861     8B2u    0.910442     8B3u    0.910442  
  13B1u    0.922798    14Ag     0.970979     8B2g    1.096867  
   8B3g    1.096867     9B2u    1.123336     9B3u    1.123336  
   4B1g    1.146944    15Ag     1.146944    14B1u    1.192648  
  10B3u    1.259153    10B2u    1.259153     5B1g    1.262085  
  16Ag     1.262085    17Ag     1.266215     4Au     1.434259  
  15B1u    1.434259     9B2g    1.578875     9B3g    1.578875  
  10B2g    1.615512    10B3g    1.615512    16B1u    1.730004  
  11B2u    1.846272    11B3u    1.846272    18Ag     1.954361  
   5Au     2.040222    17B1u    2.040222    18B1u    2.060984  
  11B2g    2.328839    11B3g    2.328839    12B3u    2.833891  
  12B2u    2.833891    19Ag     2.873567     6B1g    3.051242  
  20Ag     3.051242    13B2u    3.158270    13B3u    3.158270  
  14B3u    3.273025    14B2u    3.273025    21Ag     3.310009  
  15B3u    3.408679    15B2u    3.408679     7B1g    3.453255  
  22Ag     3.453255    12B2g    3.463784    12B3g    3.463784  
   6Au     3.597412    19B1u    3.597412    13B2g    3.670272  
  13B3g    3.670272    20B1u    3.760980     7Au     3.867702  
  21B1u    3.867702    23Ag     3.932064     8B1g    3.932064  
  22B1u    3.960406    16B2u    3.988689    16B3u    3.988689  
  24Ag     4.036124    23B1u    4.159709     8Au     4.159709  
  14B3g    4.188104    14B2g    4.188104     9B1g    4.250155  
  25Ag     4.250155    24B1u    4.260091    15B2g    4.476007  
  15B3g    4.476007    16B3g    4.517881    16B2g    4.517881  
  26Ag     4.564515    17B2u    5.387952    17B3u    5.387952  
  25B1u    5.486709     9Au     5.526009    26B1u    5.526009  
  17B3g    7.476493    17B2g    7.476493    27B1u    8.237701  
  27Ag     8.542486    10B1g    9.154386    28Ag     9.154386  
  18B3u    9.257776    18B2u    9.257776    19B2u    9.369631  
  19B3u    9.369631    18B2g    9.407756    18B3g    9.407756  
  10Au     9.852608    28B1u    9.852608    20B2u    9.931433  
  20B3u    9.931433    29Ag    10.101691    11B1g   10.101691  
  21B2u   10.102816    21B3u   10.102816    12B1g   10.116749  
  30Ag    10.116749    31Ag    10.220074    11Au    10.249144  
  29B1u   10.249144    19B3g   10.402232    19B2g   10.402232  
  30B1u   10.537000    31B1u   10.772374    12Au    10.772374  
  20B3g   11.056943    20B2g   11.056943    32Ag    11.432368  
  21B3g   12.536036    21B2g   12.536036    32B1u   12.698704  
  33Ag    37.720839    33B1u   39.087924    34Ag   113.625034  
  34B1u  113.894581  

Final Occupation by Irrep:
         Ag   B1g   B2g   B3g    Au   B1u   B2u   B3u 
DOCC [     5,    1,    2,    2,    1,    4,    2,    2 ]
SOCC [     0,    0,    0,    0,    0,    0,    0,    0 ]

Energy converged.

@DF-ROHF Final Energy: -288.32390326088102

=> Energetics <=

Nuclear Repulsion Energy =            159.1941435841582972
One-Electron Energy =                -818.7759964145514004
Two-Electron Energy =                 371.2579495695121068
Total Energy =                       -288.3239032608810248

For heavy elements the def2 basis sets have ECPs!

1 Like

In case you don’t know, ECPs (effective core potentials) replace core electrons with an effective potential to approximate how those core electrons affect the other electrons. It’s a rather good approximation to reduce the number of electrons the computer needs to deal with.

1 Like

Thank you so much for reply. But electronic energy turns out to be lower than it is. Doesn’t that affect my results?

I don’t understand your message.

The electronic energy will be far too high, but differences between energies should be barely affected. Is there a reason that you care about energies relative to zero, rather than just differences between energies?

You are absolutely right and i thank you for information :slight_smile:

this answer is enough for me thank you

This topic was automatically closed 60 days after the last reply. New replies are no longer allowed.