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Fourth order expressions for the electronic absorption lineshape of molecular excitons

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5100986· OSTI ID:1610558
 [1]
  1. City Univ. of New York (CUNY), NY (United States); DOE/OSTI
+ Show Author Affiliations
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. Finally, 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.
Research Organization:
City Univ. of New York (CUNY), NY (United States); City Univ. of New York, NY (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0001393
OSTI ID:
1610558
Alternate ID(s):
OSTI ID: 1755119
OSTI ID: 1545412
Report Number(s):
DOE-Queens--1393-25
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 151; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (1)

Special topic on dynamics of open quantum systems journal January 2020

Figures / Tables (4)

FIG. 1(p. 8)figure FIG. 1
FIG. 2(p. 8)figure FIG. 2
FIG. 3(p. 9)figure FIG. 3
FIG. 4(p. 9)figure FIG. 4

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Chemistry
Electron absorption spectroscopy
Electronic excitation
Exciton absorption lineshape
Exciton absorption lineshape
Quantum master equation
Fourth order approximation
Excitons
Fourth order approximation
Open quantum systems
Physics
Quantum coherence
Quantum master equation
Reduced-density-matrix calculation
Spectral line shape