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Two-dimensional electronic spectroscopy of beta-carotene.

Christensson, Niklas LU ; Milota, Franz; Nemeth, Alexandra; Sperling, Jaroslaw; Kauffmann, Harald F; Pullerits, Tönu LU and Hauer, Jürgen (2009) In The Journal of Physical Chemistry Part B 113(51). p.16409-16419
Abstract
Two-dimensional electronic spectroscopy (2D) has been applied to beta-carotene in solution to shine new light on the ultrafast energy dissipation network in carotenoids. The ability of 2D to relieve spectral congestion provides new experimental grounds for resolving the rise of the excited state absorption signal between 18,000 and 19,000 cm(-1). In this spectral region, the pump-probe signals from ground state bleach and stimulated emission overlap strongly. Combined modeling of the time-evolution of 2D spectra as well as comparison to published pump-probe data allow us to draw conclusions on both the electronic structure of beta-carotene as well as the spectral densities giving rise to the observed optical lineshapes. To account for the... (More)
Two-dimensional electronic spectroscopy (2D) has been applied to beta-carotene in solution to shine new light on the ultrafast energy dissipation network in carotenoids. The ability of 2D to relieve spectral congestion provides new experimental grounds for resolving the rise of the excited state absorption signal between 18,000 and 19,000 cm(-1). In this spectral region, the pump-probe signals from ground state bleach and stimulated emission overlap strongly. Combined modeling of the time-evolution of 2D spectra as well as comparison to published pump-probe data allow us to draw conclusions on both the electronic structure of beta-carotene as well as the spectral densities giving rise to the observed optical lineshapes. To account for the experimental observations on all time scales, we need to include a transition in the visible spectral range from the first optically allowed excited state (S(2)-->S(n2)). We present data from frequency resolved transient grating and pump-probe experiments confirming the importance of this transition. Furthermore, we investigate the role and nature of the S* state, controversially debated in numerous previous studies. On the basis of the analysis of Feynman diagrams, we show that the properties of S*-related signals in chi(3) techniques like pump-probe and 2D can only be accounted for if S* is an excited electronic state. Against this background, we discuss a new interpretation of pump-deplete-probe and intensity-dependent pump-probe experiments. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
113
issue
51
pages
16409 - 16419
publisher
The American Chemical Society
external identifiers
  • wos:000272713000016
  • pmid:19954155
  • scopus:72949099922
ISSN
1520-5207
DOI
10.1021/jp906604j
language
English
LU publication?
yes
id
c43b57cb-cffe-44fb-9df3-204ecec4a442 (old id 1524127)
date added to LUP
2010-01-11 13:10:41
date last changed
2017-10-29 04:06:17
@article{c43b57cb-cffe-44fb-9df3-204ecec4a442,
  abstract     = {Two-dimensional electronic spectroscopy (2D) has been applied to beta-carotene in solution to shine new light on the ultrafast energy dissipation network in carotenoids. The ability of 2D to relieve spectral congestion provides new experimental grounds for resolving the rise of the excited state absorption signal between 18,000 and 19,000 cm(-1). In this spectral region, the pump-probe signals from ground state bleach and stimulated emission overlap strongly. Combined modeling of the time-evolution of 2D spectra as well as comparison to published pump-probe data allow us to draw conclusions on both the electronic structure of beta-carotene as well as the spectral densities giving rise to the observed optical lineshapes. To account for the experimental observations on all time scales, we need to include a transition in the visible spectral range from the first optically allowed excited state (S(2)-->S(n2)). We present data from frequency resolved transient grating and pump-probe experiments confirming the importance of this transition. Furthermore, we investigate the role and nature of the S* state, controversially debated in numerous previous studies. On the basis of the analysis of Feynman diagrams, we show that the properties of S*-related signals in chi(3) techniques like pump-probe and 2D can only be accounted for if S* is an excited electronic state. Against this background, we discuss a new interpretation of pump-deplete-probe and intensity-dependent pump-probe experiments.},
  author       = {Christensson, Niklas and Milota, Franz and Nemeth, Alexandra and Sperling, Jaroslaw and Kauffmann, Harald F and Pullerits, Tönu and Hauer, Jürgen},
  issn         = {1520-5207},
  language     = {eng},
  number       = {51},
  pages        = {16409--16419},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Two-dimensional electronic spectroscopy of beta-carotene.},
  url          = {http://dx.doi.org/10.1021/jp906604j},
  volume       = {113},
  year         = {2009},
}