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

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

Alex Granovsky
gran@classic.chem.msu.su

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.
>
>
>
>
>

Tue Oct 4 '11 7:53pm

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