Phonon-Driven Femtosecond Dynamics of Excitons in Crystalline Pentacene from First Principles

Cohen, Galit; Haber, Jonah B.; Neaton, Jeffrey B.; Qiu, Diana Y.; Refaely-Abramson, Sivan

doi:10.1103/physrevlett.132.126902

Phonon-Driven Femtosecond Dynamics of Excitons in Crystalline Pentacene from First Principles

Journal Article · Wed Mar 20 00:00:00 EDT 2024 · Physical Review Letters

DOI:https://doi.org/10.1103/physrevlett.132.126902· OSTI ID:2505096

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Weizmann Institute of Science, Rehovot (Israel)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)
Yale Univ., New Haven, CT (United States)

Nonradiative exciton relaxation processes are critical for energy transduction and transport in optoelectronic materials, but how these processes are connected to the underlying crystal structure and the associated electron, exciton, and phonon band structures, as well as the interactions of all these particles, is challenging to understand. Here, in this work, we present a first-principles study of exciton-phonon relaxation pathways in pentacene, a paradigmatic molecular crystal and optoelectronic semiconductor. We compute the momentum- and band-resolved exciton-phonon interactions, and use them to analyze key scattering channels. We find that both exciton intraband scattering and interband scattering to parity-forbidden dark states occur on the same ~100 fs timescale as a direct consequence of the longitudinal-transverse splitting of the bright exciton band. Consequently, exciton-phonon scattering exists as a dominant nonradiative relaxation channel in pentacene. We further show how the propagation of an exciton wave packet is connected with crystal anisotropy, which gives rise to the longitudinal-transverse exciton splitting and concomitant anisotropic exciton and phonon dispersions. Our results provide a framework for understanding the role of exciton-phonon interactions in exciton nonradiative lifetimes in molecular crystals and beyond.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), High Energy Physics (HEP)

Grant/Contract Number:: AC02-05CH11231; SC0021965

OSTI ID:: 2505096

Alternate ID(s):: OSTI ID: 2474150

Journal Information:: Physical Review Letters, Journal Name: Physical Review Letters Journal Issue: 12 Vol. 132; ISSN 0031-9007

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Phonon-Driven Femtosecond Dynamics of Excitons in Crystalline Pentacene from First Principles

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