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Re^4: SA-CASSCF(4,4) two configuration in an one state and XMCQDPT.....

Solntsev Pasha
solntsev@univ.kiev.ua


Dear Sania.

I apologize, i didn't clarify very well. I was talking about regular unsubstituted porphyrin. This molecule indeed has D2h symmetry, you can see that very clear in electronic spectra. If you deprotonate or insert metal in it, of course you increase symmetry and due to degeneracy of LUMO (D4h) you have less number of transition in electronic spectra. But this is not my case yet. The 2nd and 3rd states lie close to each other as well as 4th and 5th. We can se that very clear from experiment. Difference not so small (~50-100 nm). I think it should be enough to separate all excitations in CASSCF job. You can correct me if i am not right.

I attached file. I used different values for wstate array in $xmcqdpt - no luck.

Thank you for you willing to help me.

Best,
Pavel.



On Wed Oct 5 '11 3:33pm, sanya wrote
------------------------------------
>I think it's OK. Probably, your structure is close to (a sort of) D4 or C4 symmetry, and these groups do have E representations. Since the symmetry is approximate, the degeneracy is approximate, too. Any asymmetric distorsion will force your molecule out of this point and remove the degeneracy.

>On Wed Oct 5 '11 1:11am, Solntsev Pasha wrote
>---------------------------------------------
>>Dear Alex.

>>Thank you for willing to help me with my proble.

>>My goal is to get excitation energies and electronic structure of the 1st and 2nd excited state of porphyrin molecule. After MCSCF i did i expected 5 states: 1st - 2200, 2nd - 2110, 3rd-2101, 4th - 1210, 5th - 1201. Or similar to that. I bu got another picture. Two configurations have almost same contribute to a state. I could expect that if we have E irrep (LUMO), but as you know in D2h we don't have E. So my question is: "Is it ok in my case?". If so how can i get reasonable data from XMCQDPT job?

>>Any advice will be accepted.

>>Best,
>>Pavel.
>>
>>
>>
>>On Tue Oct 4 '11 7:53pm, Alex Granovsky wrote
>>---------------------------------------------
>>>Dear Pasha,

>>>I would be glad to help. Could you please be a bit more specific formulating the problem itself?

>>>Kind regards,
>>>Alex Granovsky
>>>
>>>
>>>On Tue Oct 4 '11 6:44am, Solntsev Pasha wrote
>>>---------------------------------------------
>>>>Dear colleagues.

>>>>I am working on aromatic system related to porphyrin. So, i decided to check unsubstituted porphyrin by CASSCF/XMCQDPT(CASSCF(4,4)/6-311G(d,p)//b3lyp/6-311G(d,p)). I need only 1st and 2nd excited states. Their formation can be described by four orbital approach. Indeed, such approximation quite reasonable, because HOMO,HOMO-1 are separated from another HOMO's by big enough energy gap. All intense transitions in UV-Vis spectra rise from transitions HOMO->LUMO/LUMO+1, HOMO-1->LUMO/LUMO+1. In literature, people used CASPT2(4,4) method and showed such active space can be used for porphyrins (actually 4,4 is the smallest active space for such mycrocycles). So i did SS-CASSCF(4,4)+ntrack and caught all single electron excitations (4 for such active space). After optimization my 1st state was ground state and all single electron excited states were states from 2 to 5. Afterwards, i performed SA-CASSCF(4,4) over 5 lowest states ($drt wstate(1)=1,1,1,1,1 $end ) and got interesting picture(all configuration with zerro's coefficients were removed):

>>>>STATE #    1  ENERGY =    -983.487159757
>>>>
>>>>
>>>>
>>>>      CSF      COEF    OCCUPANCY (IGNORING CORE)

>>>>      ---      ----    --------- --------- -----

>>>>        1   -0.961493  2200

>>>>        4    0.113581  2002

>>>>        6    0.072134  0202

>>>>        9   -0.185355  1111

>>>>       11    0.022668  1111

>>>>       15    0.096837  2020

>>>>       17    0.103561  0220

>>>>       20   -0.049553  0022
>>>>
>>>>
>>>>
>>>> STATE #    2  ENERGY =    -983.360422516
>>>>
>>>>
>>>>
>>>>      CSF      COEF    OCCUPANCY (IGNORING CORE)

>>>>      ---      ----    --------- --------- -----

>>>>        3    0.660764  1201

>>>>        7   -0.735886  2110

>>>>       14    0.094658  0112

>>>>       18   -0.113585  1021
>>>>
>>>>
>>>> STATE #    3  ENERGY =    -983.352359738
>>>>
>>>>
>>>>
>>>>      CSF      COEF    OCCUPANCY (IGNORING CORE)

>>>>      ---      ----    --------- --------- -----

>>>>        2    0.752067  2101

>>>>        8    0.646632  1210

>>>>       13    0.105209  1012

>>>>       19    0.072064  0121
>>>>
>>>>
>>>> STATE #    4  ENERGY =    -983.286322394
>>>>
>>>>
>>>>
>>>>      CSF      COEF    OCCUPANCY (IGNORING CORE)

>>>>      ---      ----    --------- --------- -----

>>>>        3    0.708619  1201

>>>>        7    0.627084  2110

>>>>       14    0.216679  0112

>>>>       18    0.240156  1021
>>>>
>>>>
>>>> STATE #    5  ENERGY =    -983.285640465
>>>>
>>>>
>>>>
>>>>      CSF      COEF    OCCUPANCY (IGNORING CORE)

>>>>      ---      ----    --------- --------- -----

>>>>        2    0.611178  2101

>>>>        8   -0.722176  1210

>>>>       13    0.227594  1012

>>>>       19   -0.230485  0121
>>>>
>>>>
>>>>
>>>>As we can see for state #2
>>>>  3    0.660764  1201
>>>>  7   -0.735886  2110

>>>>two excitations have almost same contribution. The same thing with another states too.

>>>>I performed also XMCQDPT with different size of the H_ef but only first state from CAS-CI corresponds to first state in MCQDPT reference:
>>>>
>>>>
>>>> *** MC-XQDPT2 ENERGIES ***

>>>> -----------------------------------------------------------------------

>>>>   STATE                       1ST ORDER                       2ND ORDER

>>>>     1     E(MCSCF)=     -983.4871597547     E(MP2)=     -986.9200228420

>>>>     2     E(MCSCF)=     -983.2674851340     E(MP2)=     -986.7845079006

>>>>     3     E(MCSCF)=     -983.2459151152     E(MP2)=     -986.7769659778

>>>>     4     E(MCSCF)=     -983.2049480922     E(MP2)=     -986.7676948438

>>>>     5     E(MCSCF)=     -983.1927574918     E(MP2)=     -986.7429440001

>>>>     6     E(MCSCF)=     -983.1590205258     E(MP2)=     -986.7369602361

>>>>     7     E(MCSCF)=     -983.0694701169     E(MP2)=     -986.6898412033

>>>>     8     E(MCSCF)=     -982.8072824406     E(MP2)=     -986.5873781504

>>>> EIGENVECTORS OF THE EFFECTIVE HAMILTONIAN
>>>>
>>>>
>>>>
>>>>                      1          2          3          4          5
>>>>
>>>>
>>>>
>>>>               -986.920023-986.784508-986.776966-986.767695-986.742944
>>>>
>>>>
>>>>
>>>>    1            -0.994895  -0.067638   0.033741   0.014361   0.032678

>>>>    2            -0.067492   0.708971  -0.294819  -0.530914   0.158499

>>>>    3             0.038811   0.159120   0.755152  -0.237075   0.492123

>>>>    4            -0.030986   0.638493   0.157087   0.438907  -0.478557

>>>>    5             0.018530   0.016946  -0.563000   0.081181   0.443499

>>>>    6             0.004953  -0.211512   0.001229  -0.675617  -0.548424

>>>>    7             0.034252  -0.118795  -0.004363   0.076785   0.041466

>>>>    8             0.040266  -0.025619  -0.004813   0.011612   0.058562
>>>>
>>>>
>>>>
>>>>                      6          7          8
>>>>
>>>>
>>>>
>>>>               -986.736960-986.689841-986.587378
>>>>
>>>>
>>>>
>>>>    1             0.040499  -0.026339  -0.029372

>>>>    2            -0.270110  -0.161009   0.003527

>>>>    3             0.320243   0.031284   0.031555

>>>>    4             0.379967  -0.019337  -0.016894

>>>>    5             0.678936   0.128538   0.040542

>>>>    6             0.444792   0.005797  -0.011659

>>>>    7             0.129239  -0.953704   0.225448

>>>>    8             0.054535  -0.214298  -0.972233

>>>> EIGENVALUES OF THE NON-SYMMETRIC EFFECTIVE HAMILTONIAN
>>>>
>>>>
>>>>
>>>>     1     -986.91955413898560000000 + I *        0.00000000000000000000

>>>>     2     -986.78419407332210000000 + I *        0.00000000000000000000

>>>>     3     -986.77622935041040000000 + I *        0.00000000000000000000

>>>>     4     -986.76715735894640000000 + I *        0.00000000000000000000

>>>>     5     -986.74307507596620000000 + I *        0.00000000000000000000

>>>>     6     -986.73745642166250000000 + I *        0.00000000000000000000

>>>>     7     -986.68459320897090000000 + I *        0.00000000000000000000

>>>>     8     -986.59405552588180000000 + I *        0.00000000000000000000

>>>>OVERLAP NORM MATRIX OF NON-ORTHOGONAL EIGENVECTORS
>>>>
>>>>
>>>>
>>>>             1           2           3           4           5
>>>>
>>>>
>>>>
>>>>    1    1.0000000   0.0033939   0.0162086   0.0031617   0.0031535

>>>>    2    0.0033939   1.0000000   0.2549902   0.1426137   0.0648010

>>>>    3    0.0162086   0.2549902   1.0000000   0.1192571   0.0789034

>>>>    4    0.0031617   0.1426137   0.1192571   1.0000000   0.2513337

>>>>    5    0.0031535   0.0648010   0.0789034   0.2513337   1.0000000

>>>>    6    0.0038417   0.0901892   0.0600024   0.2513302   0.4293901

>>>>    7    0.0375041   0.0049329   0.1179925   0.0041655   0.0068307

>>>>    8    0.0448358   0.0165570   0.1067129   0.0007353   0.0019392
>>>>
>>>>
>>>>
>>>>             6           7           8
>>>>
>>>>
>>>>
>>>>    1    0.0038417   0.0375041   0.0448358

>>>>    2    0.0901892   0.0049329   0.0165570

>>>>    3    0.0600024   0.1179925   0.1067129

>>>>    4    0.2513302   0.0041655   0.0007353

>>>>    5    0.4293901   0.0068307   0.0019392

>>>>    6    1.0000000   0.0078361   0.0617392

>>>>    7    0.0078361   1.0000000   0.4620405

>>>>    8    0.0617392   0.4620405   1.0000000
>>>>
>>>>
>>>>I also played with $xmcqdpt  wstate(1) and avecoe(1) arrays. I used same as for $drt wstate(1)=1,1,1,1,1 $end but also default value for wstate from xmcqdpt.

>>>>Could you please to help me solve this problem.

>>>>If you need any extra information just let me know. I have a lot of different files related to this problem.

>>>>Best,

>>>>Pavel.
>>>>
>>>>
>>>>
>>>>
>>>>

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