Phonon-Induced Localization of Excitons in Molecular Crystals from First Principles

Alvertis, Antonios M.; Haber, Jonah B.; Engel, Edgar A.; Sharifzadeh, Sahar; Neaton, Jeffrey B.

doi:10.1103/physrevlett.130.086401

Phonon-Induced Localization of Excitons in Molecular Crystals from First Principles

Journal Article · Thu Feb 23 00:00:00 EST 2023 · Physical Review Letters

DOI:https://doi.org/10.1103/physrevlett.130.086401· OSTI ID:2293519

^[1]; ^[1]; Engel, Edgar A. ^[2]; ^[3]; Neaton, Jeffrey B. ^[4]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Univ. of Cambridge (United Kingdom). Cavendish Lab.
Boston Univ., MA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)

The spatial extent of excitons in molecular systems underpins their photophysics and utility for optoelectronic applications. Phonons are reported to lead to both exciton localization and delocalization. However, a microscopic understanding of phonon-induced (de)localization is lacking, in particular, how localized states form, the role of specific vibrations, and the relative importance of quantum and thermal nuclear fluctuations. Here, we present a first-principles study of these phenomena in solid pentacene, a prototypical molecular crystal, capturing the formation of bound excitons, exciton-phonon coupling to all orders, and phonon anharmonicity, using density functional theory, the ab initio GW-Bethe-Salpeter equation approach, finite-difference, and path integral techniques. In this study, we find that for pentacene zero-point nuclear motion causes uniformly strong localization, with thermal motion providing additional localization only for Wannier-Mott-like excitons. Anharmonic effects drive temperature-dependent localization, and, while such effects prevent the emergence of highly delocalized excitons, we explore the conditions under which these might be realized

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2293519

Journal Information:: Physical Review Letters, Journal Name: Physical Review Letters Journal Issue: 8 Vol. 130; ISSN 0031-9007

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Phonon-Induced Localization of Excitons in Molecular Crystals from First Principles

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