manuscript_revision_final.pdf (6.18 MB)
Download file

Benchmarking excited-state calculations using exciton properties

Download (6.18 MB)
journal contribution
posted on 16.03.2018, 10:39 by Stefanie A. Mewes, Felix PlasserFelix Plasser, Anna Krylov, Andreas Dreuw
© 2018 American Chemical Society. Benchmarking is an every-day task in computational chemistry, yet making meaningful comparisons between different methods is nontrivial. Benchmark studies often focus on the most obvious quantities such as energy differences. But to gain insight, it is desirable to explain the discrepancies between theoretical methods in terms of underlying wave functions and, consequently, physically relevant quantities. We present a new strategy of benchmarking excited-state calculations, which goes beyond excitation energies and oscillator strengths and involves the analysis of exciton properties based on the one-particle transition density matrix. By using this approach, we compare the performance of many-body excited-state methods (equation-of-motion coupled-cluster and algebraic diagrammatic construction) and time-dependent density functional theory. The selected examples illustrate the utility of different exciton descriptors in assigning state character and explaining the discrepancies among different methods. The examples include Rydberg, valence, and charge-transfer states, as well as delocalized excitonic states in large conjugated systems and states with substantial doubly excited character.

Funding

This work was partially supported by NSF CAREER DMS-1255422 (M.A.H.) and EPSRC grant EP/R00515X/1 (G.A.E.).

History

School

  • Science

Department

  • Chemistry

Published in

Journal of Chemical Theory and Computation

Volume

14

Issue

2

Pages

710 - 725

Citation

MEWES, S.A. ...et al., 2018. Benchmarking excited-state calculations using exciton properties. Journal of Chemical Theory and Computation, 14(2), pp. 710-725.

Publisher

© American Chemical Society (ACS)

Version

AM (Accepted Manuscript)

Publisher statement

This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/

Publication date

2018-01-11

Notes

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/10.1021/acs.jctc.7b01145.

ISSN

1549-9618

eISSN

1549-9626

Language

en

Usage metrics

Keywords

Exports