Communication: Uncovering correlated vibrational cooling and electron transfer dynamics with multidimensional spectroscopy

Analogues of 2D photon echo methods in which two population times are sampled have recently been used to expose heterogeneity in chemical kinetics. In this work, the two population times sampled for a transition metal complex are transformed into a 2D rate spectrum using the maximum entropy method....

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Bibliographic Details
Published in:The Journal of chemical physics 2016-09, Vol.145 (10)
Main Authors: Guo, Zhenkun, Giokas, Paul G., Cheshire, Thomas P., Williams, Olivia F., Dirkes, David J., You, Wei, Moran, Andrew M.
Format: Article
Language:English
Subjects:
ENGINEERING
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Summary:Analogues of 2D photon echo methods in which two population times are sampled have recently been used to expose heterogeneity in chemical kinetics. In this work, the two population times sampled for a transition metal complex are transformed into a 2D rate spectrum using the maximum entropy method. The 2D rate spectrum suggests heterogeneity in the vibrational cooling (VC) rate within the ensemble. In addition, a cross peak associated with VC and back electron transfer (BET) dynamics reveals correlation between the two processes. Here, we hypothesize that an increase in the strength of solute-solvent interactions, which accelerates VC, drives the system toward the activationless regime of BET.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4962670