Polar solvent dynamics and electron-transfer reactions

Mark Maroncelli, Jean MacInnis, Graham R. Fleming

Research output: Contribution to journalArticle

491 Citations (Scopus)

Abstract

Polar solvents often exert a dramatic influence on reactions in solution. Equilibrium aspects of this influence involve differential solvation of reactants compared to the transition state that lead to alteration of the free-energy barrier to reaction. Such effects are well known, and often give rise changes in reaction rates of many orders of magnitude. Less well understood are effects arising from non-equilibrium, dynamical aspects of solvation. During the course of reaction, charge is rapidly redistributed among reactants. How the reaction couples to its solvent environment depends critically on how fast the solvent can respond to these changes in reactant charge distribution. In this article the dynamics of solvation in polar liquids and the influence of this dynamics on electrontransfer reactions are discussed. A molecular picture suggests that polar solvation occurs on multiple time scales as a result of the involvement of different types of solvent motion. A hierarchy of models from a homogeneous continuum model to one incorporating molecular aspects of solvation, combined with computer simulations, gives insight into the underlying dynamics. Experimental measures of solvation dynamics from picosecond and subpicosecond time-dependent Stokes shift studies are compared with the predictions of theoretical models. The implication of these results for electron-transfer reactions in solution are then briefly considered.

Original languageEnglish (US)
Pages (from-to)1674-1681
Number of pages8
JournalScience
Volume243
Issue number4899
DOIs
StatePublished - Jan 1 1989

Fingerprint

Solvation
Electrons
Energy barriers
Charge distribution
Free energy
Reaction rates
Computer simulation
Liquids

All Science Journal Classification (ASJC) codes

  • General

Cite this

Maroncelli, Mark ; MacInnis, Jean ; Fleming, Graham R. / Polar solvent dynamics and electron-transfer reactions. In: Science. 1989 ; Vol. 243, No. 4899. pp. 1674-1681.
@article{d2b771a6ea914b2fad313b0ea097f366,
title = "Polar solvent dynamics and electron-transfer reactions",
abstract = "Polar solvents often exert a dramatic influence on reactions in solution. Equilibrium aspects of this influence involve differential solvation of reactants compared to the transition state that lead to alteration of the free-energy barrier to reaction. Such effects are well known, and often give rise changes in reaction rates of many orders of magnitude. Less well understood are effects arising from non-equilibrium, dynamical aspects of solvation. During the course of reaction, charge is rapidly redistributed among reactants. How the reaction couples to its solvent environment depends critically on how fast the solvent can respond to these changes in reactant charge distribution. In this article the dynamics of solvation in polar liquids and the influence of this dynamics on electrontransfer reactions are discussed. A molecular picture suggests that polar solvation occurs on multiple time scales as a result of the involvement of different types of solvent motion. A hierarchy of models from a homogeneous continuum model to one incorporating molecular aspects of solvation, combined with computer simulations, gives insight into the underlying dynamics. Experimental measures of solvation dynamics from picosecond and subpicosecond time-dependent Stokes shift studies are compared with the predictions of theoretical models. The implication of these results for electron-transfer reactions in solution are then briefly considered.",
author = "Mark Maroncelli and Jean MacInnis and Fleming, {Graham R.}",
year = "1989",
month = "1",
day = "1",
doi = "10.1126/science.243.4899.1674",
language = "English (US)",
volume = "243",
pages = "1674--1681",
journal = "Science",
issn = "0036-8075",
publisher = "American Association for the Advancement of Science",
number = "4899",

}

Polar solvent dynamics and electron-transfer reactions. / Maroncelli, Mark; MacInnis, Jean; Fleming, Graham R.

In: Science, Vol. 243, No. 4899, 01.01.1989, p. 1674-1681.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Polar solvent dynamics and electron-transfer reactions

AU - Maroncelli, Mark

AU - MacInnis, Jean

AU - Fleming, Graham R.

PY - 1989/1/1

Y1 - 1989/1/1

N2 - Polar solvents often exert a dramatic influence on reactions in solution. Equilibrium aspects of this influence involve differential solvation of reactants compared to the transition state that lead to alteration of the free-energy barrier to reaction. Such effects are well known, and often give rise changes in reaction rates of many orders of magnitude. Less well understood are effects arising from non-equilibrium, dynamical aspects of solvation. During the course of reaction, charge is rapidly redistributed among reactants. How the reaction couples to its solvent environment depends critically on how fast the solvent can respond to these changes in reactant charge distribution. In this article the dynamics of solvation in polar liquids and the influence of this dynamics on electrontransfer reactions are discussed. A molecular picture suggests that polar solvation occurs on multiple time scales as a result of the involvement of different types of solvent motion. A hierarchy of models from a homogeneous continuum model to one incorporating molecular aspects of solvation, combined with computer simulations, gives insight into the underlying dynamics. Experimental measures of solvation dynamics from picosecond and subpicosecond time-dependent Stokes shift studies are compared with the predictions of theoretical models. The implication of these results for electron-transfer reactions in solution are then briefly considered.

AB - Polar solvents often exert a dramatic influence on reactions in solution. Equilibrium aspects of this influence involve differential solvation of reactants compared to the transition state that lead to alteration of the free-energy barrier to reaction. Such effects are well known, and often give rise changes in reaction rates of many orders of magnitude. Less well understood are effects arising from non-equilibrium, dynamical aspects of solvation. During the course of reaction, charge is rapidly redistributed among reactants. How the reaction couples to its solvent environment depends critically on how fast the solvent can respond to these changes in reactant charge distribution. In this article the dynamics of solvation in polar liquids and the influence of this dynamics on electrontransfer reactions are discussed. A molecular picture suggests that polar solvation occurs on multiple time scales as a result of the involvement of different types of solvent motion. A hierarchy of models from a homogeneous continuum model to one incorporating molecular aspects of solvation, combined with computer simulations, gives insight into the underlying dynamics. Experimental measures of solvation dynamics from picosecond and subpicosecond time-dependent Stokes shift studies are compared with the predictions of theoretical models. The implication of these results for electron-transfer reactions in solution are then briefly considered.

UR - http://www.scopus.com/inward/record.url?scp=33750109348&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33750109348&partnerID=8YFLogxK

U2 - 10.1126/science.243.4899.1674

DO - 10.1126/science.243.4899.1674

M3 - Article

AN - SCOPUS:33750109348

VL - 243

SP - 1674

EP - 1681

JO - Science

JF - Science

SN - 0036-8075

IS - 4899

ER -