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arXiv · 2301.11944

Phonon-induced localization of excitons in molecular crystals from first principles

Antonios M. Alvertis·Jonah B. Haber·Edgar A. Engel·Sahar Sharifzadeh·Jeffrey B. Neaton
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Abstract

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 \emph{ab initio} $GW$-Bethe-Salpeter equation approach, finite difference, and path integral techniques. 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.

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Antonios M. Alvertis, Jonah B. Haber, Edgar A. Engel, Sahar Sharifzadeh, Jeffrey B. Neaton. 2023-01-27. Phonon-induced localization of excitons in molecular crystals from first principles. https://doi.org/10.1103/physrevlett.130.086401

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