Skip to Main content Skip to Navigation
New interface
Journal articles

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. 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 solvatochromisms of both excited states during the twisting of DMABN. This contribution stands as one of the first proofof-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.
Document type :
Journal articles
Complete list of metadata

https://hal-cnrs.archives-ouvertes.fr/hal-03854780
Contributor : Xavier Blase Connect in order to contact the contributor
Submitted on : Wednesday, November 16, 2022 - 9:18:19 AM
Last modification on : Wednesday, November 23, 2022 - 8:16:30 AM

File

JCP22-AR-02769-2.pdf
Files produced by the author(s)

Identifiers

Collections

Citation

Iryna Knysh, Ivan Duchemin, Xavier Blase, Denis Jacquemin. Modeling of excited state potential energy surfaces with the Bethe–Salpeter equation formalism: The 4-(dimethylamino)benzonitrile twist. Journal of Chemical Physics, 2022, 157 (19), pp.194102. ⟨10.1063/5.0121121⟩. ⟨hal-03854780⟩

Share

Metrics

Record views

0

Files downloads

0