Two-dimensional electronic spectroscopy of beta-carotene.
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1524127
- author
- Christensson, Niklas LU ; Milota, Franz ; Nemeth, Alexandra ; Sperling, Jaroslaw ; Kauffmann, Harald F ; Pullerits, Tönu LU and Hauer, Jürgen
- organization
- publishing date
- 2009
- 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 (ACS)
- external identifiers
-
- wos:000272713000016
- pmid:19954155
- scopus:72949099922
- pmid:19954155
- ISSN
- 1520-5207
- DOI
- 10.1021/jp906604j
- 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
- c43b57cb-cffe-44fb-9df3-204ecec4a442 (old id 1524127)
- date added to LUP
- 2016-04-01 14:58:35
- date last changed
- 2022-02-19 21:42:29
@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 (ACS)}},
series = {{The Journal of Physical Chemistry Part B}},
title = {{Two-dimensional electronic spectroscopy of beta-carotene.}},
url = {{http://dx.doi.org/10.1021/jp906604j}},
doi = {{10.1021/jp906604j}},
volume = {{113}},
year = {{2009}},
}