[molpro-user] Desired MCSCF orbital moving out of active space
Terry Frankcombe
tjf at rsc.anu.edu.au
Fri Aug 17 01:06:50 BST 2012
I have had similar experiences when trying to do specific things with
specific orbitals. To me this suggests that the orbital you are
interested in does not "contribute" much correlation energy. The
algorithm decides, rightly, that a lower energy results from rotating
your orbital of interest out of the space.
In a sense, this simply means that the optimisation algorithm in molpro
multi is "too good". The solution I have has some success with is to
hamstring the optimisation algorithm; choose a known inferior one. Try
something like:
ITERATIONS; DO AUGMENT 1 TO <whatever>
On Thu, 2012-08-16 at 16:06 +0000, 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
> _______________________________________________
> Molpro-user mailing list
> Molpro-user at molpro.net
> http://www.molpro.net/mailman/listinfo/molpro-user
More information about the Molpro-user
mailing list