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

Title: Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules

Abstract

A combination of experimental data and theoretical analysis provides evidence of a bell-shaped kinetics of electron transfer in the Arrhenius coordinates ln k vs 1/T . This kinetic law is a temperature analog of the familiar Marcus bell-shaped dependence based on ln k vs the reaction free energy. These results were obtained for reactions of intramolecular charge shift between the donor and acceptor separated by a rigid spacer studied experimentally by Miller and co-workers. The non-Arrhenius kinetic law is a direct consequence of the solvent reorganization energy and reaction driving force changing approximately as hyperbolic functions with temperature. The reorganization energy decreases and the driving force increases when temperature is increased. The point of equality between them marks the maximum of the activationless reaction rate. Reaching the consistency between the kinetic and thermodynamic experimental data requires the non-Gaussian statistics of the donor-acceptor energy gap described by the Q-model of electron transfer. Furthermore, the theoretical formalism combines the vibrational envelope of quantum vibronic transitions with the Q-model describing the classical component of the Franck-Condon factor and a microscopic solvation model of the solvent reorganization energy and the reaction free energy.

Authors:
 [1];  [2]; ORCiD logo [1]
  1. Arizona State Univ., Tempe, AZ (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Arizona State Univ., Tempe, AZ (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1349132
Alternate Identifier(s):
OSTI ID: 1345668; OSTI ID: 1349562; OSTI ID: 1352060
Report Number(s):
BNL-113671-2017-JA
Journal ID: ISSN 1520-6106
Grant/Contract Number:
SC0015641; SC00112704
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 12; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; electron transfer; bell-shaped kinetic law; Arrhenius coordinates; polar solvation; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Waskasi, Morteza M., Newton, Marshall D., and Matyushov, Dmitry V. Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules. United States: N. p., 2017. Web. doi:10.1021/acs.jpcb.7b00140.
Waskasi, Morteza M., Newton, Marshall D., & Matyushov, Dmitry V. Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules. United States. doi:10.1021/acs.jpcb.7b00140.
Waskasi, Morteza M., Newton, Marshall D., and Matyushov, Dmitry V. Thu . "Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules". United States. doi:10.1021/acs.jpcb.7b00140.
@article{osti_1349132,
title = {Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules},
author = {Waskasi, Morteza M. and Newton, Marshall D. and Matyushov, Dmitry V.},
abstractNote = {A combination of experimental data and theoretical analysis provides evidence of a bell-shaped kinetics of electron transfer in the Arrhenius coordinates ln k vs 1/T . This kinetic law is a temperature analog of the familiar Marcus bell-shaped dependence based on ln k vs the reaction free energy. These results were obtained for reactions of intramolecular charge shift between the donor and acceptor separated by a rigid spacer studied experimentally by Miller and co-workers. The non-Arrhenius kinetic law is a direct consequence of the solvent reorganization energy and reaction driving force changing approximately as hyperbolic functions with temperature. The reorganization energy decreases and the driving force increases when temperature is increased. The point of equality between them marks the maximum of the activationless reaction rate. Reaching the consistency between the kinetic and thermodynamic experimental data requires the non-Gaussian statistics of the donor-acceptor energy gap described by the Q-model of electron transfer. Furthermore, the theoretical formalism combines the vibrational envelope of quantum vibronic transitions with the Q-model describing the classical component of the Franck-Condon factor and a microscopic solvation model of the solvent reorganization energy and the reaction free energy.},
doi = {10.1021/acs.jpcb.7b00140},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 12,
volume = 121,
place = {United States},
year = {Thu Mar 16 00:00:00 EDT 2017},
month = {Thu Mar 16 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.jpcb.7b00140

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

Save / Share:
  • A combination of experimental data and theoretical analysis provides evidence of a bell-shaped kinetics of electron transfer in the Arrhenius coordinates ln k vs 1/T . This kinetic law is a temperature analog of the familiar Marcus bell-shaped dependence based on ln k vs the reaction free energy. These results were obtained for reactions of intramolecular charge shift between the donor and acceptor separated by a rigid spacer studied experimentally by Miller and co-workers. The non-Arrhenius kinetic law is a direct consequence of the solvent reorganization energy and reaction driving force changing approximately as hyperbolic functions with temperature. The reorganizationmore » energy decreases and the driving force increases when temperature is increased. The point of equality between them marks the maximum of the activationless reaction rate. Reaching the consistency between the kinetic and thermodynamic experimental data requires the non-Gaussian statistics of the donor-acceptor energy gap described by the Q-model of electron transfer. Furthermore, the theoretical formalism combines the vibrational envelope of quantum vibronic transitions with the Q-model describing the classical component of the Franck-Condon factor and a microscopic solvation model of the solvent reorganization energy and the reaction free energy.« less
  • A combination of experimental data and theoretical analysis provides evidence of a bell-shaped kinetics of electron transfer in the Arrhenius coordinates ln k vs 1/T. This kinetic law is a temperature analogue of the familiar Marcus bell-shaped dependence based on ln k vs the reaction free energy. Our results were obtained for reactions of intramolecular charge shift between the donor and acceptor separated by a rigid spacer studied experimentally by Miller and co-workers. The non-Arrhenius kinetic law is a direct consequence of the solvent reorganization energy and reaction driving force changing approximately as hyperbolic functions with temperature. Furthermore, the reorganizationmore » energy decreases and the driving force increases when temperature is increased. The point of equality between them marks the maximum of the activationless reaction rate. In reaching the consistency between the kinetic and thermodynamic experimental data requires the non-Gaussian statistics of the donor–acceptor energy gap described by the Q-model of electron transfer. The theoretical formalism combines the vibrational envelope of quantum vibronic transitions with the Q-model describing the classical component of the Franck–Condon factor and a microscopic solvation model of the solvent reorganization energy and the reaction free energy.« less
  • A combination of experimental data and theoretical analysis provides evidence of a bell-shaped kinetics of electron transfer in the Arrhenius coordinates ln k vs 1/T. This kinetic law is a temperature analogue of the familiar Marcus bell-shaped dependence based on ln k vs the reaction free energy. These results were obtained for reactions of intramolecular charge shift between the donor and acceptor separated by a rigid spacer studied experimentally by Miller and co-workers. The non-Arrhenius kinetic law is a direct consequence of the solvent reorganization energy and reaction driving force changing approximately as hyperbolic functions with temperature. The reorganization energymore » decreases and the driving force increases when temperature is increased. The point of equality between them marks the maximum of the activationless reaction rate. Reaching the consistency between the kinetic and thermodynamic experimental data requires the non-Gaussian statistics of the donor–acceptor energy gap described by the Q-model of electron transfer. The theoretical formalism combines the vibrational envelope of quantum vibronic transitions with the Q-model describing the classical component of the Franck–Condon factor and a microscopic solvation model of the solvent reorganization energy and the reaction free energy.« less
  • A systematic steady-state fluorescence and time-resolved flash photolytic investigation of a series of covalently linked fullerene/ferrocene based donor-bridge-acceptor dyads is reported as a function of the nature of the spacer between the donor site (ferrocene) and acceptor site (fullerene) and the dielectric constant of the medium. The fluorescence of the investigated dyads 2, 3, 4, 5, and 6 in methylcyclohexane at 77 K were substantially quenched, relative to N-methylfulleropyrrolidine 1, indicating intramolecular quenching of the fullerene excited singlet state. Excitation of N-methylfulleropyrrolidine revealed the immediate formation of the excited singlet state, with {lambda}{sub max} around 886 nm. A rapid intersystemmore » crossing ({tau}{sub 1/2} = 1.2 ps ) to the excited triplet state was observed with characteristic absorption around 705 nm. Picosecond resolved photolysis of dyads 2-6 in toluene showed light-induced formation of the excited singlet state which undergoes rapid intramolecular quenching. Nanosecond-resolved photolysis of dyads 3 and 4 in degassed benzonitrile revealed long-lived charge separated states with characteristic fullerene radical-anion bands at {lambda}{sub max} = 1055 nm. 30 refs., 5 figs., 3 tabs.« less
  • Cited by 3