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

Seibt, Joachim LU and Pullerits, Tönu LU (2014) In Journal of Chemical Physics 141(11).
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... (More)
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. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
141
issue
11
publisher
American Institute of Physics
external identifiers
  • pmid:25240344
  • wos:000342843200010
  • scopus:84907190255
ISSN
0021-9606
DOI
10.1063/1.4895401
language
English
LU publication?
yes
id
cf21ee73-cce3-4eae-9d9b-ccf9f5481aee (old id 4691150)
date added to LUP
2014-10-17 16:33:59
date last changed
2017-01-01 03:48:14
@article{cf21ee73-cce3-4eae-9d9b-ccf9f5481aee,
  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.},
  articleno    = {114106},
  author       = {Seibt, Joachim and Pullerits, Tönu},
  issn         = {0021-9606},
  language     = {eng},
  number       = {11},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Combined treatment of relaxation and fluctuation dynamics in the calculation of two-dimensional electronic spectra.},
  url          = {http://dx.doi.org/10.1063/1.4895401},
  volume       = {141},
  year         = {2014},
}