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Title: Understanding How Isotopes Affect Charge Transfer in P3HT/PCBM: A Quantum Trajectory-Electronic Structure Study with Nonlinear Quantum Corrections

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [1];  [2]
  1. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science and Computer Science and Mathematics Division
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The experimentally observed effect of selective deuterium substitution on the open circuit voltage for a blend of poly(3-hexylthiophene)(P3HT) and [6,6]-phenyl-C61- butyric acid methyl ester (PCBM) (Nat. Commun. 5:3180, 2014) is explored using a 221-atom model of a polymer-wrapped PCBM molecule. We describe the protonic and deuteronic wavefunctions for the H/D isotopologues of the hexyl side chains within a Quantum Trajectory/Electronic Structure approach where the dynamics is performed with newly developed nonlinear corrections to the quantum forces, necessary to describe the nuclear wavefunctions; the classical forces are generated with a Density Functional Tight Binding method. We used the resulting protonic and deuteronic time-dependent wavefunctions to assess the effects of isotopic substitution (deuteration) on the energy gaps relevant to the charge transfer for the donor and acceptor electronic states. Furthermore, while the isotope effect on the electronic energy levels is found negligible, the quantum-induced fluctuations of the energy gap between the charge transfer and charge separated states due to nuclear wavefunctions may account for experimental trends by promoting charge transfer in P3HT/PCBM and increasing charge recombination on the donor in the deuterium substituted P3HT/PCBM.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Institute for Computational Sciences (JICS)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF)
Grant/Contract Number:
AC05-00OR22725; CHE-1056188; CHE-1048629
OSTI ID:
1327594
Journal Information:
Journal of Chemical Theory and Computation, Vol. 12, Issue 9; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

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  • Valeev, Edward F.; Coropceanu, Veaceslav; da Silva Filho, Demetrio A.
  • Journal of the American Chemical Society, Vol. 128, Issue 30 https://doi.org/10.1021/ja061827h
journal August 2006
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Cited By (3)

Voltage Losses in Organic Solar Cells: Understanding the Contributions of Intramolecular Vibrations to Nonradiative Recombinations journal December 2017
A fast scheme to calculate electronic couplings between P3HT polymer units using diabatic orbitals for charge transfer dynamics simulations journal December 2018
Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics journal September 2018

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