Modeling of excited state potential energy surfaces with the Bethe–Salpeter equation formalism: The 4-(dimethylamino)benzonitrile twist

Abstract

We present a benchmark study of excited state potential energy surfaces (PES) using the many-body Green’s function GW and Bethe–Salpeter equation (BSE) formalisms, coupled cluster methods, as well as Time-Dependent Density Functional Theory (TD-DFT). More specifically, we investigate the evolution of the two lowest excited states of 4-(dimethylamino)benzonitrile (DMABN) upon the twisting of the amino group, a paradigmatic system for dual fluorescence and excited-state benchmarks. Our results demonstrate that the BSE/ GW approach is able to reproduce the correct topology of excited state PES upon geometry changes in both gas and condensed phases. The vertical transition energies predicted by BSE/ GW are indeed in good agreement with coupled cluster values, including triples. The BSE approach ability to include both linear response and state-specific solvent corrections further enables it to accurately describe the solvatochromism of both excited states during the twisting of DMABN. This contribution stands as one of the first proof-of-concept that BSE/ GW PES should be accurate in cases for which TD-DFT struggles, including the central case of systems embedded in a dielectric environment.