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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4962670· OSTI ID:1467899
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
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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.

Research Organization:
University of North Carolina, Chapel Hill, NC (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR)
Grant/Contract Number:
SC0001011; N000141410221
OSTI ID:
1467899
Alternate ID(s):
OSTI ID: 1324483
Journal Information:
Journal of Chemical Physics, Vol. 145, Issue 10; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

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