Fragment-based configuration interaction wave function to calculate environmental effect on excited states in proteins and solutions

Abstract

• Coarse-grained analysis to figure out excited-state w.f. including environments. • A fragment-based truncated CIS for the excited-state w.f. including environments. • CTs between environmental fragments give negligible contributions. Solvatochromic effect in proteins and solutions was described by a configuration interaction singles (CIS) wave function with fragment-localized molecular orbitals. Coarse-grained analysis indicated that the CI wave function can be described by local excitations and charge-transfer (CT) excitations between the chromophore and the environment. We developed an atomic-orbital direct runcated CIS code and applied the excited states of retinal chromophore in bacteriorhodopsin and MeOH environments, and those of s -trans-acrolein in water. Number of excitation operators was significantly reduced by eliminating the CT excitations between the environmental fragments. The truncated CIS wave functions reproduced the original excitation energies very well.