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

Abstract

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.

Authors:
 [1];  [1];  [1];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1544345
Alternate Identifier(s):
OSTI ID: 1414884
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 119; Journal Issue: 26; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Refaely-Abramson, Sivan, da Jornada, Felipe H., Louie, Steven G., and Neaton, Jeffrey B. Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach. United States: N. p., 2017. Web. doi:10.1103/PhysRevLett.119.267401.
Refaely-Abramson, Sivan, da Jornada, Felipe H., Louie, Steven G., & Neaton, Jeffrey B. Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach. United States. https://doi.org/10.1103/PhysRevLett.119.267401
Refaely-Abramson, Sivan, da Jornada, Felipe H., Louie, Steven G., and Neaton, Jeffrey B. Tue . "Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach". United States. https://doi.org/10.1103/PhysRevLett.119.267401. https://www.osti.gov/servlets/purl/1544345.
@article{osti_1544345,
title = {Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach},
author = {Refaely-Abramson, Sivan and da Jornada, Felipe H. and Louie, Steven G. and Neaton, Jeffrey B.},
abstractNote = {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.},
doi = {10.1103/PhysRevLett.119.267401},
journal = {Physical Review Letters},
number = 26,
volume = 119,
place = {United States},
year = {Tue Dec 26 00:00:00 EST 2017},
month = {Tue Dec 26 00:00:00 EST 2017}
}

Journal Article:

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Cited by: 44 works
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Figures / Tables:

FIG. 1. FIG. 1.: (Color online) Left panel: Excitation energies calculated at different exciton momentum for the two lowest bands of singlet and triplet excitations, where each triplet state is triply degenerate ($m$ = −1, 0, 1). The singlet states are labeled as bright (odd parity) or dark (even parity) at $Qmore » = 0$. Right panel: exciton wave functions for a hole positioned in the middle of the center molecule. The different states correspond to (top to bottom): $S_2$, $S_1$, $T_2$ and $T_1$ at $Q = 0$.« less

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Works referencing / citing this record:

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.