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:
-
- 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}
}
Web of Science
Figures / Tables:
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