[molpro-user] different SZ eigenstates for high spin states

Peter Knowles KnowlesPJ at cardiff.ac.uk
Thu Apr 23 10:44:23 BST 2015

In the case of the MRCI code, what you see in the output is certainly not associated with a particular S_z eigenvalue - instead, it is a textual representation of the branching-diagram symbol for the configuration state function. If you really wanted to expand this in determinants for a particular M_S, you would need to apply the rules for the genealogical construction of CSFs as described, for example, in Pauncz’s book.

In Multi, there are two CI programs: CSFs (as above), or determinants. In the case of the latter, the desired S quantum number is used to specify the M_S quantum number. If you really wanted to get the wavefunction for a different M_S then you would need to apply the angular momentum lowering operator.


> On 23 Apr 2015, at 10:09, anikodem at ulg.ac.be wrote:
> Dear Molpro Users and Developers,
> When calculating the spin-orbit matrix for the spin orbit coupling one sees that
> Molpro uses all possible SZ eigenstates for each spin (S) eigenstate.
> However when showing configurations for the states, for example the CI vectors
> in the MRCI calculation, it only shows the eigenstates for the highest SZ state.
> We want to calculate quadruplets (S=1.5) corresponding to SZ=0.5. Molpro only provides
> us with results for SZ=1.5. 
> Does anyone know a parameter or a way to get the configuration for the CI method or
> the Multi program for other SZ eigenstates? So that we can get the coefficients of the configurations 
> for the  states with spin S = 1.5 and SZ = 0.5 directly? 
> Many thanks for your help,
> Astrid Nikodem
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Prof. Peter J. Knowles             
School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
Telephone: +44 29 208 79182
Email: KnowlesPJ at Cardiff.ac.uk 

Yr Athro Peter J. Knowles
Yr Ysgol Cemeg, Prifysgol Caerdydd,
Prif Adeilad, Plas y Parc
Caerdydd CF10 3AT, DU
Ffôn: +44 2920 879182
Ebost: KnowlesPJ at Caerdydd.ac.uk
Ysgrifennwch ataf yn Gymraeg neu Saesneg

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