Issue 19, 2018

The Bethe–Salpeter formalism with polarisable continuum embedding: reconciling linear-response and state-specific features

Abstract

The Bethe–Salpeter equation (BSE) formalism has been recently shown to be a valuable alternative to time-dependent density functional theory (TD-DFT) with the same computing time scaling with system size. In particular, problematic transitions for TD-DFT such as charge-transfer, Rydberg and cyanine-like excitations were shown to be accurately described with BSE. We demonstrate here that combining the BSE formalism with the polarisable continuum model (PCM) allows us to include simultaneously linear-response and state-specific contributions to solvatochromism. This is confirmed by exploring transitions of various natures (local, charge-transfer, etc.) in a series of solvated molecules (acrolein, indigo, p-nitro-aniline, donor–acceptor complexes, etc.) for which we compare BSE solvatochromic shifts to those obtained by linear-response and state-specific TD-DFT implementations. Such a remarkable and unique feature is particularly valuable for the study of solvent effects on excitations presenting a hybrid localised/charge-transfer character.

Graphical abstract: The Bethe–Salpeter formalism with polarisable continuum embedding: reconciling linear-response and state-specific features

Supplementary files

Article information

Article type
Edge Article
Submitted
01 Feb 2018
Accepted
02 Apr 2018
First published
05 Apr 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 4430-4443

The Bethe–Salpeter formalism with polarisable continuum embedding: reconciling linear-response and state-specific features

I. Duchemin, C. A. Guido, D. Jacquemin and X. Blase, Chem. Sci., 2018, 9, 4430 DOI: 10.1039/C8SC00529J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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