Intruder state problem

Anugraha · Yesterday 07:20:54

Dear Molcas developres,
I am running a CASPT2 calculation on a molecule of 34 atoms for the ground and pi pi star state with state average=2. In CASPT2 section i used the IPEA shift of 0.0 and imaginary shift of 0.2. Iam attaching the output for both states :

++ CASPT2 computation for group 1

********************************************************************************
Multi-State initialization phase begins for group 1
--------------------------------------------------------------------------------
********************************************************************************
Compute H0 matrices for state 1
--------------------------------------------------------------------------------
--------------------------------------------------------------------------------
H0 matrices have been computed.

********************************************************************************
CASPT2 EQUATION SOLUTION
--------------------------------------------------------------------------------

Total nr of CASPT2 parameters:
Before reduction: 147120531
After reduction: 147093568

Variance of |WF0>: 9.9713419736

The contributions to the second order correlation energy in atomic units.
-----------------------------------------------------------------------------------------------------------------------------
IT. VJTU VJTI ATVX AIVX VJAI BVAT BJAT BJAI TOTAL RNORM
-----------------------------------------------------------------------------------------------------------------------------
1 -0.000117 -0.004188 -0.021622 -0.142950 -0.039870 -0.042941 -0.236665 -2.048814 -2.537167 0.003581
2 -0.000119 -0.004231 -0.021735 -0.143430 -0.039963 -0.042964 -0.236757 -2.048933 -2.538131 0.000278
3 -0.000119 -0.004231 -0.021735 -0.143439 -0.039963 -0.042964 -0.236764 -2.048932 -2.538147 0.000032
4 -0.000119 -0.004231 -0.021734 -0.143437 -0.039962 -0.042964 -0.236763 -2.048931 -2.538142 0.000004
-----------------------------------------------------------------------------------------------------------------------------

FINAL CASPT2 RESULT:

Reference energy: -834.6646225709
E2 (Non-variational): -2.5381418967
Shift correction: -0.0114617216
E2 (Variational): -2.5496036183
Total energy: -837.2142261892
Residual norm: 0.0000003924
Reference weight: 0.56232

Contributions to the CASPT2 correlation energy
Active & Virtual Only: -0.0646987605
One Inactive Excited: -0.3803183944
Two Inactive Excited: -2.0931247417

++ Denominators, etc.
--------------------------------------------------------------------------------------------------------------
Report on small energy denominators, large coefficients, and large energy contributions.
CASE SYMM ACTIVE-MIX NON-ACTIVE INDICES DENOMINATOR RHS VALUE COEFFICIENT CONTRIBUTION
ATVX 2 Mu2.0001 Se2.016 0.16446750 0.00008876 -0.00020242 -0.00000002
ATVX 2 Mu2.0002 Se2.016 0.27735004 0.00002079 -0.00005411 -0.00000000
ATVX 2 Mu2.0001 Se2.017 0.17676048 -0.00024815 0.00048589 -0.00000012
ATVX 2 Mu2.0002 Se2.017 0.28964301 0.00008247 -0.00006209 -0.00000001
ATVX 2 Mu2.0001 Se2.018 0.18436255 0.00007372 -0.00015557 -0.00000001
ATVX 2 Mu2.0002 Se2.018 0.29724508 -0.00002671 0.00008128 -0.00000000
ATVX 2 Mu2.0001 Se2.019 0.22307446 0.00049866 -0.00057109 -0.00000028
ATVX 2 Mu2.0001 Se2.020 0.24566379 -0.00150156 0.00258428 -0.00000388
ATVX 2 Mu2.0001 Se2.021 0.25352261 0.00099156 -0.00187405 -0.00000186
ATVX 2 Mu2.0001 Se2.022 0.26443001 0.00134464 -0.00289140 -0.00000389
ATVX 2 Mu2.0001 Se2.023 0.27701460 -0.00029005 0.00052980 -0.00000015
ATVX 2 Mu2.0001 Se2.024 0.29303259 -0.00002871 -0.00013942 0.00000000
--

++ CASPT2 computation for group 2

********************************************************************************
Multi-State initialization phase begins for group 2
--------------------------------------------------------------------------------
********************************************************************************
Compute H0 matrices for state 2
--------------------------------------------------------------------------------
--------------------------------------------------------------------------------
H0 matrices have been computed.

********************************************************************************
CASPT2 EQUATION SOLUTION
--------------------------------------------------------------------------------

Total nr of CASPT2 parameters:
Before reduction: 147120531
After reduction: 147093237

Variance of |WF0>: 9.9816542846

The contributions to the second order correlation energy in atomic units.
-----------------------------------------------------------------------------------------------------------------------------
IT. VJTU VJTI ATVX AIVX VJAI BVAT BJAT BJAI TOTAL RNORM
-----------------------------------------------------------------------------------------------------------------------------
1 -0.000245 -0.004377 -0.030462 -0.154639 -0.040314 -0.043576 -0.249608 -2.048717 -2.571937 0.003830
2 -0.000252 -0.004414 -0.030648 -0.155099 -0.040388 -0.043606 -0.249694 -2.048815 -2.572916 0.000428
3 -0.000253 -0.004415 -0.030651 -0.155121 -0.040388 -0.043605 -0.249706 -2.048815 -2.572953 0.000062
4 -0.000253 -0.004415 -0.030650 -0.155115 -0.040387 -0.043605 -0.249705 -2.048813 -2.572942 0.000010
5 -0.000253 -0.004415 -0.030650 -0.155115 -0.040387 -0.043605 -0.249704 -2.048813 -2.572941 0.000001
-----------------------------------------------------------------------------------------------------------------------------

FINAL CASPT2 RESULT:

Reference energy: -834.4670908832
E2 (Non-variational): -2.5729416160
Shift correction: -0.0144302163
E2 (Variational): -2.5873718323
Total energy: -837.0544627155
Residual norm: 0.0000002124
Reference weight: 0.54873

Contributions to the CASPT2 correlation energy
Active & Virtual Only: -0.0742548589
One Inactive Excited: -0.4050719958
Two Inactive Excited: -2.0936147613

++ Denominators, etc.
--------------------------------------------------------------------------------------------------------------
Report on small energy denominators, large coefficients, and large energy contributions.
CASE SYMM ACTIVE-MIX NON-ACTIVE INDICES DENOMINATOR RHS VALUE COEFFICIENT CONTRIBUTION
VJTU 1 Mu1.0001 In1.040 0.28826619 -0.00023808 0.00054682 -0.00000013
VJTU 1 Mu1.0001 In1.041 0.27160881 -0.00012096 0.00031980 -0.00000004
VJTU 1 Mu1.0001 In1.042 0.26373035 0.00054436 -0.00130574 -0.00000071
VJTU 1 Mu1.0001 In1.043 0.25786633 0.00049647 -0.00122700 -0.00000061
VJTU 1 Mu1.0001 In1.044 0.23124537 -0.00011624 0.00035927 -0.00000004
VJTU 1 Mu1.0001 In1.045 0.20563966 -0.00014160 0.00039057 -0.00000006
VJTU 1 Mu1.0001 In1.046 0.19157691 -0.00003328 0.00015648 -0.00000001
VJTU 1 Mu1.0001 In1.047 0.18257418 0.00001161 -0.00004071 -0.00000000
VJTU 1 Mu1.0001 In1.048 0.16579633 -0.00016593 0.00040110 -0.00000007
VJTU 1 Mu1.0001 In1.049 0.15775315 0.00006336 -0.00016799 -0.00000001
VJTU 1 Mu1.0001 In1.050 0.10953556 -0.00005837 0.00019011 -0.00000001
VJTU 1 Mu1.0001 In1.051 0.07215227 -0.00006768 0.00010926 -0.00000001
VJTU 1 Mu1.0002 In1.051 0.26433715 -0.00004682 0.00009822 -0.00000000
VJTU 1 Mu1.0003 In1.051 0.27761824 0.00000181 -0.00000569 -0.00000000
VJTU 2 Mu2.0002 In2.002 0.28595473 -0.00011096 0.00028088 -0.00000003
VJTU 2 Mu2.0002 In2.003 0.26695007 -0.00021717 0.00062262 -0.00000014
VJTU 2 Mu2.0002 In2.004 0.23524463 -0.00289273 0.00860890 -0.00002490
VJTU 2 Mu2.0002 In2.005 0.13955562 -0.00020618 0.00053011 -0.00000011
VJTU 2 Mu2.0003 In2.005 0.27710224 -0.00001438 -0.00003110 0.00000000
VJTU 2 Mu2.0002 In2.006 0.11406939 0.00030984 -0.00071436 -0.00000022
VJTU 2 Mu2.0003 In2.006 0.25161601 0.00006513 -0.00032434 -0.00000002
VJTU 2 Mu2.0002 In2.007 0.09454723 -0.00037575 0.00089308 -0.00000034
VJTU 2 Mu2.0003 In2.007 0.23209384 -0.00036545 0.00094391 -0.00000034
VJTU 2 Mu2.0004 In2.007 0.29040915 0.00023695 -0.00041696 -0.00000010
VJTU 2 Mu2.0002 In2.008 0.08825529 -0.00116927 0.00260660 -0.00000305
VJTU 2 Mu2.0003 In2.008 0.22580191 -0.00133027 0.00352419 -0.00000469
VJTU 2 Mu2.0004 In2.008 0.28411722 0.00067203 -0.00112012 -0.00000075
ATVX 1 Mu1.0001 Se1.053 0.03797839 0.00001329 -0.00001051 -0.00000000
ATVX 1 Mu1.0002 Se1.053 0.21607240 -0.00001179 0.00002632 -0.00000000
ATVX 1 Mu1.0003 Se1.053 0.21667996 -0.00000306 0.00000745 -0.00000000
ATVX 1 Mu1.0001 Se1.054 0.04753370 -0.00005124 0.00005456 -0.00000000
ATVX 1 Mu1.0002 Se1.054 0.22562772 0.00003763 -0.00008840 -0.00000000
ATVX 1 Mu1.0003 Se1.054 0.22623528 0.00000053 -0.00000158 -0.00000000
ATVX 1 Mu1.0001 Se1.055 0.05521549 0.00000190 -0.00000240 -0.00000000
ATVX 1 Mu1.0002 Se1.055 0.23330951 -0.00000154 0.00000369 -0.00000000
ATVX 1 Mu1.0003 Se1.055 0.23391707 -0.00000012 0.00000006 -0.00000000
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With this how do i know intruder states are present or not. If intruder states are present which shift i have to use. (I have avoided the IPEA shift because of the paper 'The IPEA Dilemma in CASPT2').

I would be really thankful if anyone can help me to solve this issue.

Thank you
Anugraha

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Intruder state problem

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