Effective Fragment Potentials for Microsolvated Excited and Anionic States

The effective fragment potential (EFP) approach is a sophisticated hybrid approach that allows the inclusion of solvation effects when describing properties and reactivity in the condensed phase, without using empirical parameters. This work examines the performance of the EFP method when describing microsolvation in electronically excited states of neutrals and anions. The examples selected include both localized valence states, as well as diffuse nonvalence states, which represent greater challenges to conventional electronic structure methods. The equation-of-motion coupled cluster with singles and doubles (EOM-XX-CCSD) methodology has been used to provide the quantum chemical description of both the full microsolvated clusters, and the chromophoric moiety in mixed quantum/EFP calculations. We find that, when averaging over multiple configurations of microsolvated clusters, the differences between QM/EFP and full quantum results are minimal, although individual configurations often have larger errors. As expected, diffuse states have somewhat larger errors, although not significantly so. The close proximity of states leading to mixing can make QM/EFP less accurate because a change of ordering of states can occur. Other properties, such as photoelectron images and lifetimes of metastable states, are very well described for the monohydrated clusters investigated.

Automated summary

The EFP approach is an effective method for including solvation effects in condensed phase properties and reactivity. This study examines the performance of the EFP method in describing microsolvation in electronically excited states. The results show minimal differences between QM/EFP and full quantum results when averaging over multiple configurations of microsolvated clusters, although individual configurations may have larger errors. Diffuse states have slightly larger errors, and QM/EFP may be less accurate in capturing state ordering changes. However, other properties such as photoelectron images and lifetimes are well described by the method.