skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. 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) (SC-22); 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. doi: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. doi: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 = {2016},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Heterogeneity of the Electron-Trapping Kinetics in CdSe Nanoparticles
journal, August 2011

  • Kern, Sean J.; Sahu, Kalyanasis; Berg, Mark A.
  • Nano Letters, Vol. 11, Issue 8
  • DOI: 10.1021/nl202086b

Outer-sphere electron transfer in polar solvents
journal, July 1980


Two-dimensional optical spectroscopy of excitons in semiconductor quantum wells: Liouville-space pathway analysis
journal, March 2007


Two-dimensional infrared spectroscopy of peptides by phase-controlled femtosecond vibrational photon echoes
journal, July 2000

  • Asplund, M. C.; Zanni, M. T.; Hochstrasser, R. M.
  • Proceedings of the National Academy of Sciences, Vol. 97, Issue 15
  • DOI: 10.1073/pnas.140227997

Ultrafast Spectroscopic Signatures of Coherent Electron-Transfer Mechanisms in a Transition Metal Complex
journal, July 2016

  • Guo, Zhenkun; Giokas, Paul G.; Cheshire, Thomas P.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 29
  • DOI: 10.1021/acs.jpca.6b04313

Quantum effects in electron transfer reactions with strong electronic coupling
journal, December 1994

  • Stuchebrukhov, Alexei A.; Song, Xueyu
  • The Journal of Chemical Physics, Vol. 101, Issue 11
  • DOI: 10.1063/1.468444

Vibrational Anharmonicities Revealed by Coherent Two-Dimensional Infrared Spectroscopy
journal, March 2001


Energy Transfer between Localized Electronic States –From Non-Adiabatic to Adiabatic Hopping Limits–
journal, November 1980

  • Sumi, Hitoshi
  • Journal of the Physical Society of Japan, Vol. 49, Issue 5
  • DOI: 10.1143/JPSJ.49.1701

Rate and Amplitude Heterogeneity in the Solvation Response of an Ionic Liquid
journal, January 2016

  • Verma, Sachin Dev; Corcelli, Steven A.; Berg, Mark A.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 3
  • DOI: 10.1021/acs.jpclett.5b02835

Two-dimensional spectroscopy using diffractive optics based phased-locked photon echoes
journal, March 2004


Rate Dispersion in the Biexciton Decay of CdSe/ZnS Nanoparticles from Multiple Population-Period Transient Spectroscopy
journal, January 2013

  • Sahu, Kalyanasis; Wu, Haorui; Berg, Mark A.
  • Journal of the American Chemical Society, Vol. 135, Issue 3
  • DOI: 10.1021/ja3112109

T WO -D IMENSIONAL F EMTOSECOND S PECTROSCOPY
journal, October 2003


Solvation dynamics in electron-transfer, isomerization, and nonlinear optical processes: a unified Liouville-space theory
journal, August 1988

  • Yan, Yi Jing; Sparpaglione, Massimo; Mukamel, Shaul
  • The Journal of Physical Chemistry, Vol. 92, Issue 17
  • DOI: 10.1021/j100328a010

Two-dimensional electronic spectroscopy and photosynthesis: Fundamentals and applications to photosynthetic light-harvesting
journal, July 2011


Vibrational Relaxation Dynamics in Solutions
journal, October 1994


Coherence in Energy Transfer and Photosynthesis
journal, April 2015


Parallels between multiple population-period transient spectroscopy and multidimensional coherence spectroscopies
journal, August 2008

  • Khurmi, Champak; Berg, Mark A.
  • The Journal of Chemical Physics, Vol. 129, Issue 6
  • DOI: 10.1063/1.2960589

Probing Photosynthetic Energy and Charge Transfer with Two-Dimensional Electronic Spectroscopy
journal, January 2012

  • Lewis, Kristin L. M.; Ogilvie, Jennifer P.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 4
  • DOI: 10.1021/jz201592v

Heterogeneous Reaction Rates in an Ionic Liquid: Quantitative Results from Two-Dimensional Multiple Population-Period Transient Spectroscopy
journal, July 2011

  • Sahu, Kalyanasis; Kern, Sean J.; Berg, Mark A.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 27
  • DOI: 10.1021/jp2046068

Exciton−Exciton Correlations Revealed by Two-Quantum, Two-Dimensional Fourier Transform Optical Spectroscopy
journal, September 2009

  • Stone, Katherine W.; Turner, Daniel B.; Gundogdu, Kenan
  • Accounts of Chemical Research, Vol. 42, Issue 9
  • DOI: 10.1021/ar900122k

Dynamical effects in electron transfer reactions
journal, May 1986

  • Sumi, H.; Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 84, Issue 9
  • DOI: 10.1063/1.449978

Elucidation of reactive wavepackets by two-dimensional resonance Raman spectroscopy
journal, September 2015

  • Guo, Zhenkun; Molesky, Brian P.; Cheshire, Thomas P.
  • The Journal of Chemical Physics, Vol. 143, Issue 12
  • DOI: 10.1063/1.4931473

Phase-stabilized two-dimensional electronic spectroscopy
journal, September 2004

  • Brixner, Tobias; Mančal, Tomáš; Stiopkin, Igor V.
  • The Journal of Chemical Physics, Vol. 121, Issue 9
  • DOI: 10.1063/1.1776112

Comparison of Electron Transfer Dynamics in Molecule-to-Nanoparticle and Intramolecular Charge Transfer Complexes
journal, September 2003

  • Wang, Yuhuang; Hang, Kun; Anderson, Neil A.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 35
  • DOI: 10.1021/jp034935o

Multiresonant Coherent Multidimensional Spectroscopy
journal, May 2011


On the Rate Distribution Analysis of Kinetic Data Using the Maximum Entropy Method:  Applications to Myoglobin Relaxation on the Nanosecond and Femtosecond Timescales
journal, August 2001

  • Kumar, Anand T. N.; Zhu, Leyun; Christian, J. F.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 32
  • DOI: 10.1021/jp0101209

Measuring a hidden coordinate: Rate-exchange kinetics from 3D correlation functions
journal, August 2016

  • Berg, Mark A.; Darvin, Jason R.
  • The Journal of Chemical Physics, Vol. 145, Issue 5
  • DOI: 10.1063/1.4960186

Time-Resolved Optical Spectroscopy with Multiple Population Dimensions: A General Method for Resolving Dynamic Heterogeneity
journal, August 2007

  • van Veldhoven, Emile; Khurmi, Champak; Zhang, Xinzheng
  • ChemPhysChem, Vol. 8, Issue 12
  • DOI: 10.1002/cphc.200700088

Synthetic, structural, and physical studies of titanium complexes of catechol and 3,5-di-tert-butylcatechol
journal, April 1984

  • Borgias, Brandan A.; Cooper, Stephen R.; Koh, Yun Bai
  • Inorganic Chemistry, Vol. 23, Issue 8
  • DOI: 10.1021/ic00176a005

Contemporary Issues in Electron Transfer Research
journal, January 1996

  • Barbara, Paul F.; Meyer, Thomas J.; Ratner, Mark A.
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp9605663