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The symmetrical quasi-classical approach to electronically nonadiabatic dynamics applied to ultrafast exciton migration processes in semiconducting polymers

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5037815· OSTI ID:1543869
 [1];  [1];  [2];  [2];  [2];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Goethe Univ. Frankfurt, Frankfurt/Main (Germany)
+ Show Author Affiliations
In the last several years, a symmetrical quasi-classical (SQC) windowing model applied to the classical Meyer-Miller (MM) vibronic Hamiltonian has been shown to be a simple, efficient, general, and quite-accurate method for treating electronically nonadiabatic processes at the totally classical level. Here, the SQC/MM methodology is applied to ultrafast exciton dynamics in a Frenkel/site-exciton model of oligothiophene (OT) as a model of organic semiconductor polymers. In order to keep the electronic representation as compact and efficient as possible, the adiabatic version of the MM Hamiltonian was employed, with dynamical calculations carried out in the recently developed “kinematic momentum” representation, from which site/monomer-specific (diabatic) excitation probabilities were extracted using a new procedure developed in this work. The SQC/MM simulation results are seen to describe coherent exciton transport driven by planarization of a central torsion defect in the OT oligomer as well as to capture exciton self-trapping effects in good agreement with benchmark quantum calculations using the multi-layer multiconfiguration time-dependent Hartree approach. The SQC/MM calculations are also seen to significantly outperform the standard Ehrenfest approach, which shows serious discrepancies. Furthermore, these results are encouraging, not only because they illustrate a significant further application of the SQC/MM approach and its utility, but because they strongly suggest that classical mechanical simulations (with the potential for linear scaling efficiency) can be used to capture, quantitatively, important dynamical features of electronic excitation energy transfer in semiconducting polymers.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1543869
Alternate ID(s):
OSTI ID: 1461248
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 149; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (10)

Solving the Trivial Crossing Problem While Preserving the Nodal Symmetry of the Wave Function journal June 2019
Combining Meyer–Miller Hamiltonian with electronic structure methods for on-the-fly nonadiabatic dynamics simulations: implementation and application journal January 2019
Initial sampling in symmetrical quasiclassical dynamics based on Li–Miller mapping Hamiltonian journal January 2019
First-principles quantum simulations of exciton diffusion on a minimal oligothiophene chain at finite temperature journal January 2020
Performance evaluation of the symmetrical quasi-classical dynamics method based on Meyer-Miller mapping Hamiltonian in the treatment of site-exciton models journal November 2018
Torsionally induced exciton localization and decoherence in π -conjugated polymers journal December 2018
A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states journal March 2019
A new perspective for nonadiabatic dynamics with phase space mapping models journal July 2019
Performance Evaluation of the Symmetrical Quasi-Classical Dynamics Method based on Meyer-Miller Mapping Hamiltonian in the Treatment of Site-Exciton Models text January 2018
Initial Sampling in Symmetrical Quasiclassical Dynamics Based on Li-Miller Mapping Hamiltonian text January 2018

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