Vol.:(0123456789)
Topics in Current Chemistry (2018) 376:35
https://doi.org/10.1007/s41061-018-0213-4
1 3
REVIEW
Multidimensional Vibrational Coherence Spectroscopy
Tiago Buckup
1
· Jérémie Léonard
2
Received: 12 April 2018 / Accepted: 31 July 2018
© Springer Nature Switzerland AG 2018
Abstract
Multidimensional vibrational coherence spectroscopy has been part of laser spectroscopy since the 1990s and its role in several areas of science has continuously
been increasing. In this contribution, after introducing the principals of vibrational
coherence spectroscopy (VCS), we review the three most widespread experimental methods for multidimensional VCS (multi-VCS), namely femtosecond stimulated Raman spectroscopy, pump-impulsive vibrational spectroscopy, and pumpdegenerate four wave-mixing. Focus is given to the generation and typical analysis
of the respective signals in the time and spectral domains. Critical aspects of all
multidimensional techniques are the challenges in the data interpretation due to
the existence of several possible contributions to the observed signals or to optical interferences and how to overcome the corresponding difficulties by exploiting
experimental parameters including higher-order nonlinear effects. We overview how
multidimensional vibrational coherence spectroscopy can assist a chemist in understanding how molecular structural changes and eventually photochemical reactions
take place. In order to illustrate the application of the techniques described in this
chapter, two molecular systems are discussed in more detail in regard to the vibrational dynamics in the electronic excited states: (1) carotenoids as a non-reactive
system and (2) stilbene derivatives as a reactive system.
Keywords Ultrafast laser spectroscopy · Multidimensional spectroscopy · Raman ·
Vibrational spectroscopy · Coherence spectroscopy · Excited states · Vibronic
coupling · Photoisomerization
* Tiago Buckup
tiago.buckup@pci.uni-heidelberg.de
Jérémie Léonard
jeremie.leonard@ipcms.unistra.fr
1
Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229,
69120 Heidelberg, Germany
2
Université de Strasbourg, CNRS, Institut de Physique et Chimie des Matériaux de Strasbourg,
UMR 7504, and Labex NIE, 67034 Strasbourg, France
207
Reprinted from the journal
Chapter 5 was originally published as Buckup, T. & Léonard, J. Topics in Current Chemistry (2018)
376: 35. https://doi.org/10.1007/s41061-018-0213-4.
Topics in Current Chemistry (2018) 376:35
https://doi.org/10.1007/s41061-018-0213-4
1 3
REVIEW
Multidimensional Vibrational Coherence Spectroscopy
Tiago Buckup
1
· Jérémie Léonard
2
Received: 12 April 2018 / Accepted: 31 July 2018
© Springer Nature Switzerland AG 2018
Abstract
Multidimensional vibrational coherence spectroscopy has been part of laser spectroscopy since the 1990s and its role in several areas of science has continuously
been increasing. In this contribution, after introducing the principals of vibrational
coherence spectroscopy (VCS), we review the three most widespread experimental methods for multidimensional VCS (multi-VCS), namely femtosecond stimulated Raman spectroscopy, pump-impulsive vibrational spectroscopy, and pumpdegenerate four wave-mixing. Focus is given to the generation and typical analysis
of the respective signals in the time and spectral domains. Critical aspects of all
multidimensional techniques are the challenges in the data interpretation due to
the existence of several possible contributions to the observed signals or to optical interferences and how to overcome the corresponding difficulties by exploiting
experimental parameters including higher-order nonlinear effects. We overview how
multidimensional vibrational coherence spectroscopy can assist a chemist in understanding how molecular structural changes and eventually photochemical reactions
take place. In order to illustrate the application of the techniques described in this
chapter, two molecular systems are discussed in more detail in regard to the vibrational dynamics in the electronic excited states: (1) carotenoids as a non-reactive
system and (2) stilbene derivatives as a reactive system.
Keywords Ultrafast laser spectroscopy · Multidimensional spectroscopy · Raman ·
Vibrational spectroscopy · Coherence spectroscopy · Excited states · Vibronic
coupling · Photoisomerization
* Tiago Buckup
tiago.buckup@pci.uni-heidelberg.de
Jérémie Léonard
jeremie.leonard@ipcms.unistra.fr
1
Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229,
69120 Heidelberg, Germany
2
Université de Strasbourg, CNRS, Institut de Physique et Chimie des Matériaux de Strasbourg,
UMR 7504, and Labex NIE, 67034 Strasbourg, France
207
Reprinted from the journal
Chapter 5 was originally published as Buckup, T. & Léonard, J. Topics in Current Chemistry (2018)
376: 35. https://doi.org/10.1007/s41061-018-0213-4.