7.12 Restricted Active Space Spin-Flip (RAS-SF) and Configuration Interaction (RAS-CI)

7.12.4 Excitonic Analysis of the RAS-CI Wave Function

(May 16, 2021)

The RAS-CI wave function of multi-chromophoric systems can be decomposed in terms of local excitations (LE), charge resonances (CR) and multi-exciton configurations (ME).

|Ψ=|ΨLE+|ΨCR+|ΨME (7.114)

The wave function decomposition scheme combines the use of fragment (localized) orbitals with the computation of charge and spin cumulant indexes. 700 Luzanov A. V. et al.
J. Chem. Phys.
(2015), 142, pp. 224104.
, 162 Casanova D., Krylov A. I.
J. Chem. Phys.
(2016), 144, pp. 014102.
Such analysis is extremely useful in order to characterize in great detail the nature of the ground and excited states in the presence of two or more molecules or chromophoric moieties. The ME contributions can be further decomposed into different spin coupled configurations localized on each. Typically, the ME part of a singlet state in a molecular dimer can be decomposed as singlet-singlet (SS) and triplet-tripled (TT) contributions.

|ΨME|ΨSS+|ΨTT (7.115)

At the moment, this analysis is only available for the decomposition of spin singlet states.