Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach

Refaely-Abramson, Sivan; da Jornada, Felipe H.; Louie, Steven G.; Neaton, Jeffrey B.

doi:10.1103/PhysRevLett.119.267401

Title: Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach

Journal Article · 26 December 2017 · Physical Review Letters

DOI: https://doi.org/10.1103/PhysRevLett.119.267401 · OSTI ID:1544345

Refaely-Abramson, Sivan ^[1]; da Jornada, Felipe H. ^[1]; Louie, Steven G. ^[1]; Neaton, Jeffrey B. ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

We develop a new first-principles approach to predict and understand rates of singlet fission with an ab initio Green's-function formalism based on many-body perturbation theory. Starting with singlet and triplet excitons computed from a GW plus Bethe-Salpeter equation approach, we calculate the exciton--bi-exciton coupling to lowest order in the Coulomb interaction, assuming a final state consisting of two non-interacting spin-correlated triplets with finite center-of-mass momentum. For crystalline pentacene, symmetries dictate that the only purely Coulombic fission decay from a bright singlet state requires a final state consisting of two inequivalent nearly degenerate triplets of nonzero, equal and opposite, center-of-mass momenta. For such a process, we predict a singlet lifetime of 40 to 150 fs, in very good agreement with experimental data, indicating that this process can dominate singlet fission in crystalline pentacene. As a result, our approach is general and provides a framework for predicting and understanding multiexciton interactions in solids.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1544345

Alternate ID(s):: OSTI ID: 1414884

Journal Information:: Physical Review Letters, Vol. 119, Issue 26; ISSN 0031-9007

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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