R E V I E W
Two-Dimensional Resonance Raman Signatures
of Vibronic Coherence Transfer in Chemical Reactions
Zhenkun Guo
1 • Brian P. Molesky
1 • Thomas P. Cheshire
1 •
Andrew M. Moran
1
Received: 11 April 2017 / Accepted: 2 October 2017 / Published online: 2 November 2017
Ó Springer International Publishing AG 2017
Abstract Two-dimensional resonance Raman (2DRR) spectroscopy has been
developed for studies of photochemical reaction mechanisms and structural
heterogeneity in condensed phase systems. 2DRR spectroscopy is motivated by
knowledge of non-equilibrium effects that cannot be detected with traditional resonance Raman spectroscopy. For example, 2DRR spectra may reveal correlated
distributions of reactant and product geometries in systems that undergo chemical
reactions on the femtosecond time scale. Structural heterogeneity in an ensemble
may also be reflected in the 2D spectroscopic line shapes of both reactive and nonreactive systems. In this chapter, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of
triiodide. We show that signatures of ‘‘vibronic coherence transfer’’ in the photodissociation process can be targeted with particular 2DRR pulse sequences. Key
differences between the signal generation mechanisms for 2DRR and off-resonant
2D Raman spectroscopy techniques are also addressed. Overall, recent experimental
developments and applications of the 2DRR method suggest that it will be a
valuable tool for elucidating ultrafast chemical reaction mechanisms.
Keywords Multidimensional spectroscopy Á Raman spectroscopy Á Ultrafast
spectroscopy Á Photodissociation Á Coherence transfer
& Andrew M. Moran
ammoran@email.unc.edu
1
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599,
USA
123
Top Curr Chem (Z) (2017) 375:87
https://doi.org/10.1007/s41061-017-0173-0
247
Reprinted from the journal
Chapter 6 was originally published as Guo, Z., Molesky, B. P., Cheshire, T. P. & Moran, A. M. Top Curr
Chem (Z) (2017) 375: 87. https://doi.org/10.1007/s41061-017-0173-0.
Two-Dimensional Resonance Raman Signatures
of Vibronic Coherence Transfer in Chemical Reactions
Zhenkun Guo
1 • Brian P. Molesky
1 • Thomas P. Cheshire
1 •
Andrew M. Moran
1
Received: 11 April 2017 / Accepted: 2 October 2017 / Published online: 2 November 2017
Ó Springer International Publishing AG 2017
Abstract Two-dimensional resonance Raman (2DRR) spectroscopy has been
developed for studies of photochemical reaction mechanisms and structural
heterogeneity in condensed phase systems. 2DRR spectroscopy is motivated by
knowledge of non-equilibrium effects that cannot be detected with traditional resonance Raman spectroscopy. For example, 2DRR spectra may reveal correlated
distributions of reactant and product geometries in systems that undergo chemical
reactions on the femtosecond time scale. Structural heterogeneity in an ensemble
may also be reflected in the 2D spectroscopic line shapes of both reactive and nonreactive systems. In this chapter, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of
triiodide. We show that signatures of ‘‘vibronic coherence transfer’’ in the photodissociation process can be targeted with particular 2DRR pulse sequences. Key
differences between the signal generation mechanisms for 2DRR and off-resonant
2D Raman spectroscopy techniques are also addressed. Overall, recent experimental
developments and applications of the 2DRR method suggest that it will be a
valuable tool for elucidating ultrafast chemical reaction mechanisms.
Keywords Multidimensional spectroscopy Á Raman spectroscopy Á Ultrafast
spectroscopy Á Photodissociation Á Coherence transfer
& Andrew M. Moran
ammoran@email.unc.edu
1
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599,
USA
123
Top Curr Chem (Z) (2017) 375:87
https://doi.org/10.1007/s41061-017-0173-0
247
Reprinted from the journal
Chapter 6 was originally published as Guo, Z., Molesky, B. P., Cheshire, T. P. & Moran, A. M. Top Curr
Chem (Z) (2017) 375: 87. https://doi.org/10.1007/s41061-017-0173-0.