[molpro-user] Desired MCSCF orbital moving out of active space
Peter Knowles
KnowlesPJ at Cardiff.ac.uk
Fri Aug 17 07:02:01 BST 2012
Perhaps try
restrict,0,1,3.5
to stop the 3 sigma_u orbital becoming merely a correlating orbital?
Peter
http://www.molpro.net/info/current/doc/quickstart/node17.html
http://www.molpro.net/info/current/doc/manual/node229.html
On 16 Aug 2012, at 17:06, Little, Duncan wrote:
> Dear Molpro users,
>
> I am trying to generate orbitals using MULTI for use in a separate calculation. I have previously posted about this: http://www.molpro.net/pipermail/molpro-user/2012-July/004968.html (thank you for your responses) but now feel I have refined my problem. The problem I am experiencing is that an orbital that is needed for a particular (Rydberg) state in my separate calculation is constantly pushed above the active space orbitals every time I try to increase the active space to incorporate it. I use the same active space for the separate calculation as the MOLPRO one for generating the orbitals. For example:
>
> 31102110 CAS, the orbital I would like to be in the active space is highlighted by ****. It is the first virtual orbital after the active orbitals:
>
> angstrom
> geometry={
> N,, 0.0000000, 0.00000000, r,; N,, 0.0000000, 0.00000000, -r,;
> }
>
> {rhf
> wf,charge=1,symmetry=1,spin=1;}
>
> {mcscf
> config
> CLOSED,1,0,0,0,1,0,0,0,
> occ,3,1,1,0,2,1,1,0;
> }
> wf,charge=1,symmetry=1,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=2,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=3,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=5,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=6,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=7,spin=1;state,1;weight,1;
> ORBPRINT,110}
>
>
> NATURAL ORBITALS
> ================
>
> Orb Occ Energy Coefficients
> 1.5 2.00000 -16.127629 0.992816 0.000121 0.018420 -0.009890 0.005998 0.000584 -0.001178 -0.000138 0.002840 -0.002171
> -0.000081 0.000261 0.000000 -0.000380 0.000000 -0.000908 0.000000 0.000344 0.000000 -0.000018
> 0.000000 0.000087 0.000000 0.000252 0.000000 -0.000067 0.000000 0.000000 0.000057 0.000000
> 0.000000
>
> 2.5 1.74152 -1.093616 0.007334 0.343864 0.283056 0.632141 0.353841 -0.036050 0.080350 0.155758 0.160042 0.002537
> 0.006503 -0.002890 0.000000 -0.006509 0.000000 -0.003557 0.000000 0.003376 0.000000 0.000340
> 0.000000 -0.000493 0.000000 0.000567 0.000000 -0.000049 0.000000 0.000000 -0.000722 0.000000
> 0.000000
>
> **** 3.5 -0.00000 -0.082578 -0.001345 -0.059745 -0.000497 -0.499029 -4.563792-10.178761 -0.007343 -0.022340 0.460257 2.317907
> 2.931892 0.004592 0.000000 -0.029487 -0.000000 -0.242067 -0.000000 -0.418116 -0.000000 0.000852
> 0.000000 0.028458 0.000000 0.036191 0.000000 -0.002525 0.000000 0.000000 -0.003243 -0.000000
> -0.000000
>
> 4.5 -0.00000 0.064433 -0.014736 -0.110028 -0.261324 0.916306 13.950224 33.887139 -0.006373 0.010013 -1.576450 -7.800327
> -6.758397 -0.008343 -0.000000 0.122852 0.000000 0.860659 0.000000 1.388081 0.000000 -0.004092
> -0.000000 -0.100116 -0.000000 -0.092591 -0.000000 0.009613 -0.000000 -0.000000 0.005993 0.000000
> 0.000000
>
> 5.5 -0.00000 0.184409 0.007943 -0.020624 -0.010409 0.329126 9.566157 2.631699 0.034462 0.107873 -0.598887 -3.426771
> -0.612603 0.000287 0.000000 0.060834 0.000000 0.428530 0.000000 2.382657 0.000000 -0.001865
> 0.000000 -0.018177 -0.000000 -0.363481 -0.000000 -0.006317 0.000000 -0.000000 0.047744 -0.000000
> 0.000000
>
> -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
>
> Separate calculation. Increasing the active space to 31103110, the orbital then moves to 4.5 (again highlighted by ****).
>
> {mcscf
> config
> CLOSED,1,0,0,0,1,0,0,0,
> occ,3,1,1,0,3,1,1,0;
> wf,charge=1,symmetry=1,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=2,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=3,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=5,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=6,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=7,spin=1;state,1;weight,1;
> ORBPRINT,110}
>
> NATURAL ORBITALS
> ================
>
> Orb Occ Energy Coefficients
>
> 1.5 2.00000 -16.116798 0.992724 0.000033 0.018523 -0.009949 0.006088 0.000623 -0.001119 -0.000248 0.002746 -0.002229
> -0.000087 0.000264 0.000000 -0.000318 0.000000 -0.000885 0.000000 0.000350 0.000000 -0.000025
> 0.000000 0.000058 0.000000 0.000251 0.000000 -0.000057 0.000000 0.000000 0.000066 0.000000
> 0.000000
>
> 2.5 1.72734 -1.087097 0.007619 0.344272 0.282977 0.634465 0.353815 -0.035906 0.080098 0.155189 0.159046 0.002279
> 0.006469 -0.002711 0.000000 -0.005941 0.000000 -0.002921 0.000000 0.003430 0.000000 0.000462
> 0.000000 -0.000255 0.000000 0.000588 0.000000 -0.000068 0.000000 0.000000 -0.000748 0.000000
> 0.000000
>
> 3.5 0.01910 0.678758 -0.045703 -0.347049 -0.397846 -0.973099 -0.704256 -0.193372 0.285598 0.660047 0.831059 0.300589
> 0.028733 0.014519 0.000000 0.009487 0.000000 -0.086907 0.000000 -0.030679 0.000000 -0.001631
> 0.000000 0.000472 0.000000 0.010586 0.000000 -0.001806 0.000000 0.000000 0.003928 0.000000
> 0.000000
>
> **** 4.5 -0.00000 -0.079708 -0.000612 0.038633 -0.019481 0.455560 4.697201 10.697348 0.022228 0.053456 -0.431397 -2.373266
> -3.050646 -0.003252 0.000000 0.036710 0.000000 0.267211 0.000000 0.458377 0.000000 -0.001136
> 0.000000 -0.030899 -0.000000 -0.039953 -0.000000 0.002579 -0.000000 -0.000000 0.003774 0.000000
> 0.000000
>
> ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
>
>
> Separate calculation. Increasing the active space to 31104110 (I am aware this may not be an ideal CAS but it is solely to illustrate my point), the orbital then moves to 4.5 (again highlighted by ****).
>
> {rhf
> wf,charge=1,symmetry=1,spin=1;}
>
> {mcscf
> config
> CLOSED,1,0,0,0,1,0,0,0,
> occ,3,1,1,0,4,1,1,0;
> wf,charge=1,symmetry=1,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=2,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=3,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=5,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=6,spin=1;state,1;weight,1;
> wf,charge=1,symmetry=7,spin=1;state,1;weight,1;
> ORBPRINT,110}
>
>
>
>
> NATURAL ORBITALS
> ================
>
> Orb Occ Energy Coefficients
> 1.5 2.00000 -16.116631 0.992710 0.000036 0.018568 -0.009984 0.006086 0.000608 -0.001132 -0.000246 0.002772 -0.002235
> -0.000085 0.000265 0.000000 -0.000325 0.000000 -0.000894 0.000000 0.000351 0.000000 -0.000024
> 0.000000 0.000060 0.000000 0.000254 0.000000 -0.000057 0.000000 0.000000 0.000066 0.000000
> 0.000000
>
> 2.5 1.72897 -1.087327 0.007169 0.341606 0.280128 0.623621 0.377514 -0.027605 0.079566 0.153830 0.158453 0.001259
> 0.005524 -0.002652 0.000000 -0.006146 0.000000 -0.003580 0.000000 0.003723 0.000000 0.000469
> 0.000000 -0.000277 0.000000 0.000759 0.000000 -0.000060 0.000000 0.000000 -0.000700 0.000000
> 0.000000
>
> 3.5 0.01915 0.692432 -0.040626 -0.321662 -0.357695 -0.917013 -0.889834 -0.209679 0.295834 0.683983 0.808532 0.322875
> 0.030401 0.016586 0.000000 0.010275 0.000000 -0.087661 0.000000 -0.035449 0.000000 -0.000774
> 0.000000 0.002678 0.000000 0.009216 0.000000 -0.002156 0.000000 0.000000 0.003225 0.000000
> 0.000000
>
> 4.5 0.00307 0.796155 -0.083489 -0.513488 -1.211317 0.066232 3.073560 0.258293 -0.118911 -0.311993 0.001787 -0.556182
> -0.029572 -0.017016 0.000000 -0.025841 0.000000 0.009608 0.000000 0.086108 0.000000 -0.006459
> 0.000000 -0.014354 0.000000 0.019845 0.000000 0.003748 0.000000 0.000000 0.003494 0.000000
> 0.000000
>
> ***** 5.5 -0.00000 -0.042134 0.008871 0.032148 0.127032 -0.475218 -7.748323-19.960582 0.005297 0.000261 0.835343 3.953541
> 4.903763 0.005937 -0.000000 -0.058749 -0.000000 -0.432178 -0.000000 -0.718211 -0.000000 0.002261
> -0.000000 0.052030 0.000000 0.061429 0.000000 -0.004754 0.000000 0.000000 -0.005687 -0.000000
> -0.000000
>
>
>
>
> Does any one have any idea what may be causing this or what it is indicative of? I've tried a variety of orbital restrictions, increasing the CAS in other symmetries but the orbital constantly jumps up in everything I do.
>
> Any suggestions would be much appreciated.
>
> Duncan Little
>
> University College London
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--
Prof. Peter J. Knowles
School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
Email KnowlesPJ at Cardiff.ac.uk
WWW http://www.cardiff.ac.uk/chemy/contactsandpeople/academicstaff/knowles.html
Secretary: Alison Thompson, ThompsonAF at Cardiff.ac.uk Telephone +44 29 208 74805
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