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Title: Combined treatment of relaxation and fluctuation dynamics in the calculation of two-dimensional electronic spectra

Abstract

While the theoretical description of population transfer subsequent to electronic excitation in combination with a line shape function description of vibrational dynamics in the context of 2D-spectroscopy is well-developed under the assumption of different timescales of population transfer and fluctuation dynamics, the treatment of the interplay between both kinds of processes lacks a comprehensive description. To bridge this gap, we use the cumulant expansion approach to derive response functions, which account for fluctuation dynamics and population transfer simultaneously. We compare 2D-spectra of a model system under different assumptions about correlations between fluctuations and point out under which conditions a simplified treatment is justified. Our study shows that population transfer and dissipative fluctuation dynamics cannot be described independent of each other in general. Advantages and limitations of the proposed calculation method and its compatibility with the modified Redfield description are discussed.

Authors:
;  [1]
  1. Department of Chemical Physics, Lund University, Box 124, SE-2100 Lund (Sweden)
Publication Date:
OSTI Identifier:
22308398
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 11; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CALCULATION METHODS; EXCITATION; FLUCTUATIONS; RELAXATION; RESPONSE FUNCTIONS; SPECTRA; SPECTROSCOPY

Citation Formats

Seibt, Joachim, and Pullerits, Tõnu. Combined treatment of relaxation and fluctuation dynamics in the calculation of two-dimensional electronic spectra. United States: N. p., 2014. Web. doi:10.1063/1.4895401.
Seibt, Joachim, & Pullerits, Tõnu. Combined treatment of relaxation and fluctuation dynamics in the calculation of two-dimensional electronic spectra. United States. doi:10.1063/1.4895401.
Seibt, Joachim, and Pullerits, Tõnu. Sun . "Combined treatment of relaxation and fluctuation dynamics in the calculation of two-dimensional electronic spectra". United States. doi:10.1063/1.4895401.
@article{osti_22308398,
title = {Combined treatment of relaxation and fluctuation dynamics in the calculation of two-dimensional electronic spectra},
author = {Seibt, Joachim and Pullerits, Tõnu},
abstractNote = {While the theoretical description of population transfer subsequent to electronic excitation in combination with a line shape function description of vibrational dynamics in the context of 2D-spectroscopy is well-developed under the assumption of different timescales of population transfer and fluctuation dynamics, the treatment of the interplay between both kinds of processes lacks a comprehensive description. To bridge this gap, we use the cumulant expansion approach to derive response functions, which account for fluctuation dynamics and population transfer simultaneously. We compare 2D-spectra of a model system under different assumptions about correlations between fluctuations and point out under which conditions a simplified treatment is justified. Our study shows that population transfer and dissipative fluctuation dynamics cannot be described independent of each other in general. Advantages and limitations of the proposed calculation method and its compatibility with the modified Redfield description are discussed.},
doi = {10.1063/1.4895401},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 11,
volume = 141,
place = {United States},
year = {2014},
month = {9}
}