Molcas Forum

lwang

Member

Registered: 2024-10-14

Posts: 16

The electronic state is deflected when calculating the Caspt2 energy

I used Molcas to calculate the guanine anion Caspt2 energy in a PCM water solvent when the electronic state was deflected。But the multiwfn software is correct to check the orbitals from the ground state to the second excited state, which are all Π antibond orbitals, and the calculated VEA value is also correct, what is the reason for this?

The input files are as follows:

&GATEWAY
coord =g.XYZ
 basis =Aug-cc-pvdz
 group = C1
 RF-input
 PCM-model; solvent= water
 End of RF-input
 RICD
>>> EXPORT MOLCAS_MAXITER = 500
&SEWARD
    DoAnalytical
&RASSCF
   FILEORB =g.3.RasOrb
   Charge =-1
   spin=2
   nActEl=13 0 0
   Ras2=12
   ciroot =1 1 1
&CASPT2
  Maxit =500
  Lroot = 1
  RFPert
&RASSCF
   Charge =-1
   spin=2
   nActEl=13 0 0
   Ras2=12
   ciroot =8 8 1
   NONEquilibrium
&CASPT2
   Maxit =500
   Multistate=3 1 2 3
   RFPert

The output file is as follows:

++ Mixed CI coefficients:
  The CI coefficients for the MIXED state nr.   1
--------------------------------------------------------------------------------
 CI COEFFICIENTS LARGER THAN  0.50D-01
  Occupation of active orbitals, and spin coupling
  of open shells. (u,d: Spin up or down).
  SGUGA info is (Midvert:IsyUp:UpperWalk/LowerWalk)
        Conf  SGUGA info        Occupation       Coefficient         Weight
           1  ( 1:1:   1/   1)   222222u00000      -0.137429       0.018887
           2  ( 1:1:   2/   1)   2222220u0000      -0.864922       0.748090
           4  ( 1:1:   4/   1)   222222000u00      -0.234929       0.055191
          11  ( 2:1:   5/   1)   22222ud0u000      -0.051285       0.002630
          13  ( 2:1:   7/   1)   22222uu0d000      -0.057112       0.003262
          20  ( 2:1:  14/   1)   22222u0u0d00       0.075944       0.005768
          22  ( 2:1:  16/   1)   22222u000200       0.163187       0.026630
         152  ( 2:1:   2/   5)   2u2222du0000       0.052810       0.002789
         160  ( 2:1:  10/   5)   2u2222d00u00       0.094529       0.008936
         166  ( 2:1:  16/   5)   2u2222000200       0.070945       0.005033
         187  ( 2:1:   1/   6)   u22222200000       0.071521       0.005115
         223  ( 3:1:   1/   1)   2222202u0000       0.085171       0.007254
         241  ( 3:1:  19/   1)   2222200u0200      -0.058839       0.003462
        1059  ( 3:1:  67/  12)   2220220u0002      -0.062368       0.003890

  The CI coefficients for the MIXED state nr.   2
--------------------------------------------------------------------------------
 CI COEFFICIENTS LARGER THAN  0.50D-01
  Occupation of active orbitals, and spin coupling
  of open shells. (u,d: Spin up or down).
  SGUGA info is (Midvert:IsyUp:UpperWalk/LowerWalk)
        Conf  SGUGA info        Occupation       Coefficient         Weight
           1  ( 1:1:   1/   1)   222222u00000       0.843594       0.711651
           2  ( 1:1:   2/   1)   2222220u0000      -0.220449       0.048598
           4  ( 1:1:   4/   1)   222222000u00       0.323214       0.104467
           7  ( 2:1:   1/   1)   22222u200000       0.101616       0.010326
          11  ( 2:1:   5/   1)   22222ud0u000      -0.073787       0.005445
          22  ( 2:1:  16/   1)   22222u000200      -0.052491       0.002755
         224  ( 3:1:   2/   1)   222220u20000       0.052840       0.002792
         240  ( 3:1:  18/   1)   222220u00200       0.072884       0.005312
        1058  ( 3:1:  66/  12)   222022u00002       0.060873       0.003705

  The CI coefficients for the MIXED state nr.   3
--------------------------------------------------------------------------------
 CI COEFFICIENTS LARGER THAN  0.50D-01
  Occupation of active orbitals, and spin coupling
  of open shells. (u,d: Spin up or down).
  SGUGA info is (Midvert:IsyUp:UpperWalk/LowerWalk)
        Conf  SGUGA info        Occupation       Coefficient         Weight
           1  ( 1:1:   1/   1)   222222u00000      -0.354767       0.125860
           2  ( 1:1:   2/   1)   2222220u0000      -0.135533       0.018369
           3  ( 1:1:   3/   1)   22222200u000       0.086723       0.007521
           4  ( 1:1:   4/   1)   222222000u00       0.820539       0.673284
          16  ( 2:1:  10/   1)   22222ud00u00      -0.067477       0.004553
          17  ( 2:1:  11/   1)   22222u0d0u00       0.057570       0.003314
          19  ( 2:1:  13/   1)   22222uu00d00      -0.163199       0.026634
          20  ( 2:1:  14/   1)   22222u0u0d00      -0.090735       0.008233
          22  ( 2:1:  16/   1)   22222u000200       0.054082       0.002925
         152  ( 2:1:   2/   5)   2u2222du0000      -0.066024       0.004359
         160  ( 2:1:  10/   5)   2u2222d00u00       0.055072       0.003033
         202  ( 2:1:  16/   6)   u22222000200      -0.078254       0.006124
         231  ( 3:1:   9/   1)   222220200u00      -0.094673       0.008963
         233  ( 3:1:  11/   1)   222220020u00      -0.061769       0.003815
        1061  ( 3:1:  69/  12)   222022000u02       0.057634       0.003322

Last edited by lwang (2025-03-27 04:52:52)