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Title: 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. 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.
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0001011; N000141410221
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 10; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of North Carolina, Chapel Hill, NC (United States)
Sponsoring Org:
USDOE; US Department of the Navy, Office of Naval Research (ONR)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 42 ENGINEERING
OSTI Identifier:
1467899
Alternate Identifier(s):
OSTI ID: 1324483