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Potential pitfalls of the early-time dynamics in two-dimensional electronic spectroscopy

Paleček, David LU ; Edlund, Petra; Gustavsson, Emil; Westenhoff, Sebastian LU and Zigmantas, Donatas LU (2019) In Journal of Chemical Physics 151(2).
Abstract

Two-dimensional electronic spectroscopy, and especially the polarization-controlled version of it, is the cutting edge technique for disentangling various types of coherences in molecules and molecular aggregates. In order to evaluate the electronic coherences, which often decay on a 100 fs time scale, the early population times have to be included in the analysis. However, signals in this region are typically plagued by several artifacts, especially in the unavoidable pulse overlap region. In this paper, we show that, in the case of polarization-controlled two-dimensional spectroscopy experiment, the early-time dynamics can be dominated by the "incorrect" pulse ordering signals. These signals can affect kinetics at positive times well... (More)

Two-dimensional electronic spectroscopy, and especially the polarization-controlled version of it, is the cutting edge technique for disentangling various types of coherences in molecules and molecular aggregates. In order to evaluate the electronic coherences, which often decay on a 100 fs time scale, the early population times have to be included in the analysis. However, signals in this region are typically plagued by several artifacts, especially in the unavoidable pulse overlap region. In this paper, we show that, in the case of polarization-controlled two-dimensional spectroscopy experiment, the early-time dynamics can be dominated by the "incorrect" pulse ordering signals. These signals can affect kinetics at positive times well beyond the pulse overlap region, especially when the "correct" pulse ordering signals are much weaker. Moreover, the "incorrect" pulse ordering contributions are oscillatory and overlap with the spectral signatures of energy transfer, which may lead to misinterpretation of "incorrect" pulse ordering signals for fast-decaying coherences.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
151
issue
2
publisher
American Institute of Physics
external identifiers
  • scopus:85068770114
ISSN
0021-9606
DOI
10.1063/1.5079817
language
English
LU publication?
yes
id
3fba4048-4501-415d-9507-1711a80e39ee
date added to LUP
2019-07-23 10:51:56
date last changed
2019-08-14 04:42:17
@article{3fba4048-4501-415d-9507-1711a80e39ee,
  abstract     = {<p>Two-dimensional electronic spectroscopy, and especially the polarization-controlled version of it, is the cutting edge technique for disentangling various types of coherences in molecules and molecular aggregates. In order to evaluate the electronic coherences, which often decay on a 100 fs time scale, the early population times have to be included in the analysis. However, signals in this region are typically plagued by several artifacts, especially in the unavoidable pulse overlap region. In this paper, we show that, in the case of polarization-controlled two-dimensional spectroscopy experiment, the early-time dynamics can be dominated by the "incorrect" pulse ordering signals. These signals can affect kinetics at positive times well beyond the pulse overlap region, especially when the "correct" pulse ordering signals are much weaker. Moreover, the "incorrect" pulse ordering contributions are oscillatory and overlap with the spectral signatures of energy transfer, which may lead to misinterpretation of "incorrect" pulse ordering signals for fast-decaying coherences.</p>},
  articleno    = {024201},
  author       = {Paleček, David and Edlund, Petra and Gustavsson, Emil and Westenhoff, Sebastian and Zigmantas, Donatas},
  issn         = {0021-9606},
  language     = {eng},
  month        = {07},
  number       = {2},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Potential pitfalls of the early-time dynamics in two-dimensional electronic spectroscopy},
  url          = {http://dx.doi.org/10.1063/1.5079817},
  volume       = {151},
  year         = {2019},
}