Communication: Uncovering correlated vibrational cooling and electron transfer dynamics with multidimensional spectroscopy
Abstract
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:
-
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- University of North Carolina, Chapel Hill, NC (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR)
- OSTI Identifier:
- 1467899
- Alternate Identifier(s):
- OSTI ID: 1324483
- Grant/Contract Number:
- SC0001011; N000141410221
- Resource 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)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 42 ENGINEERING
Citation Formats
Guo, Zhenkun, Giokas, Paul G., Cheshire, Thomas P., Williams, Olivia F., Dirkes, David J., You, Wei, and Moran, Andrew M. Communication: Uncovering correlated vibrational cooling and electron transfer dynamics with multidimensional spectroscopy. United States: N. p., 2016.
Web. doi:10.1063/1.4962670.
Guo, Zhenkun, Giokas, Paul G., Cheshire, Thomas P., Williams, Olivia F., Dirkes, David J., You, Wei, & Moran, Andrew M. Communication: Uncovering correlated vibrational cooling and electron transfer dynamics with multidimensional spectroscopy. United States. https://doi.org/10.1063/1.4962670
Guo, Zhenkun, Giokas, Paul G., Cheshire, Thomas P., Williams, Olivia F., Dirkes, David J., You, Wei, and Moran, Andrew M. Wed .
"Communication: Uncovering correlated vibrational cooling and electron transfer dynamics with multidimensional spectroscopy". United States. https://doi.org/10.1063/1.4962670. https://www.osti.gov/servlets/purl/1467899.
@article{osti_1467899,
title = {Communication: Uncovering correlated vibrational cooling and electron transfer dynamics with multidimensional spectroscopy},
author = {Guo, Zhenkun and Giokas, Paul G. and Cheshire, Thomas P. and Williams, Olivia F. and Dirkes, David J. and You, Wei and Moran, Andrew M.},
abstractNote = {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.},
doi = {10.1063/1.4962670},
journal = {Journal of Chemical Physics},
number = 10,
volume = 145,
place = {United States},
year = {Wed Sep 14 00:00:00 EDT 2016},
month = {Wed Sep 14 00:00:00 EDT 2016}
}
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