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Title: Fourth order expressions for the electronic absorption lineshape of molecular excitons

Abstract

The line shape of electronic absorption spectroscopy reflects the information on quantum dynamical processes accompanying the electronic excitation, and its accurate description is an important component for validating theoretical models and assumptions. The present work provides detailed expressions for the absorption line shape of molecular excitons that are valid up to the fourth order of exciton-bath interactions within the quantum master equation approach. These expressions can serve as the basis for developing general and systematic methods to model the line shape for a broad class of molecular exciton systems and environments. For the bath model of linearly coupled harmonic oscillators, more detailed expressions employing the spectral densities of the bath are presented. These expressions are then tested for a linear aggregate of identical chromophores each coupled to the harmonic oscillator bath. Calculation results for a super-Ohmic spectral density with exponential cutoff demonstrate the feasibility of calculations and also offer insights into the utility and difficulty of going beyond the second order approximation.

Authors:
ORCiD logo [1]
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  1. City Univ. of New York (CUNY), NY (United States)
Publication Date:
Research Org.:
City Univ. of New York (CUNY), NY (United States); City Univ. of New York, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE
OSTI Identifier:
1610558
Alternate Identifier(s):
OSTI ID: 1545412; OSTI ID: 1755119
Report Number(s):
DOE-Queens-1393-25
Journal ID: ISSN 0021-9606; TRN: US2105652
Grant/Contract Number:  
SC0001393; CHE-1362926
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Chemistry; Physics; Exciton absorption lineshape; Quantum master equation; Fourth order approximation; Open quantum systems; Electronic excitation; Excitons; Reduced-density-matrix calculation; Electron absorption spectroscopy; Spectral line shape; Quantum coherence; Exciton absorption lineshape, Quantum master equation, Fourth order approximation

Citation Formats

Jang, Seogjoo J. Fourth order expressions for the electronic absorption lineshape of molecular excitons. United States: N. p., 2019. Web. doi:10.1063/1.5100986.
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Jang, Seogjoo J. Fourth order expressions for the electronic absorption lineshape of molecular excitons. United States. https://doi.org/10.1063/1.5100986
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Jang, Seogjoo J. Mon . "Fourth order expressions for the electronic absorption lineshape of molecular excitons". United States. https://doi.org/10.1063/1.5100986. https://www.osti.gov/servlets/purl/1610558.
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@article{osti_1610558,
title = {Fourth order expressions for the electronic absorption lineshape of molecular excitons},
author = {Jang, Seogjoo J.},
abstractNote = {The line shape of electronic absorption spectroscopy reflects the information on quantum dynamical processes accompanying the electronic excitation, and its accurate description is an important component for validating theoretical models and assumptions. The present work provides detailed expressions for the absorption line shape of molecular excitons that are valid up to the fourth order of exciton-bath interactions within the quantum master equation approach. These expressions can serve as the basis for developing general and systematic methods to model the line shape for a broad class of molecular exciton systems and environments. For the bath model of linearly coupled harmonic oscillators, more detailed expressions employing the spectral densities of the bath are presented. These expressions are then tested for a linear aggregate of identical chromophores each coupled to the harmonic oscillator bath. Calculation results for a super-Ohmic spectral density with exponential cutoff demonstrate the feasibility of calculations and also offer insights into the utility and difficulty of going beyond the second order approximation.},
doi = {10.1063/1.5100986},
journal = {Journal of Chemical Physics},
number = 4,
volume = 151,
place = {United States},
year = {Mon Jul 29 00:00:00 EDT 2019},
month = {Mon Jul 29 00:00:00 EDT 2019}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.5100986
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Cited by: 2 works
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Figures / Tables:

FIG. 1 FIG. 1: Absorption line shapes for J0 = −200 and Γfl = 10 at kBT = 200 in the units of $\hbar$ = c = 1, and Å as unit length, for η = 0.2 and 0.5 and for Nc = 3 and 6. QME2 represents the 2nd order QMEmore » calculation result, and QME4 represents the 4th order QME calculation result. “Diagonal approx.” represents the approximation, Eq. (72), which includes only the diagonal components of the exciton-bath coupling in the exciton basis.« less
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    Special topic on dynamics of open quantum systems
    journal, January 2020

    • Berkelbach, Timothy C.; Thoss, Michael
    • The Journal of Chemical Physics, Vol. 152, Issue 2
    • DOI: 10.1063/1.5142731
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