Combined treatment of relaxation and fluctuation dynamics in the calculation of two-dimensional electronic spectra.
(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:
https://lup.lub.lu.se/record/4691150
- author
- Seibt, Joachim LU and Pullerits, Tönu LU
- organization
- publishing date
- 2014
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Chemical Physics
- volume
- 141
- issue
- 11
- article number
- 114106
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- pmid:25240344
- wos:000342843200010
- scopus:84907190255
- ISSN
- 0021-9606
- DOI
- 10.1063/1.4895401
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
- id
- cf21ee73-cce3-4eae-9d9b-ccf9f5481aee (old id 4691150)
- date added to LUP
- 2016-04-01 10:40:39
- date last changed
- 2022-01-26 01:24:38
@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.}},
author = {{Seibt, Joachim and Pullerits, Tönu}},
issn = {{0021-9606}},
language = {{eng}},
number = {{11}},
publisher = {{American Institute of Physics (AIP)}},
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}},
doi = {{10.1063/1.4895401}},
volume = {{141}},
year = {{2014}},
}