10. Intermolecular Electron Transfer Reactivity for Organic Compounds Studied Using Marcus Cross-Rate Theory

  1. Herbert DaCosta and
  2. Maohong Fan
  1. Stephen F. Nelsen1 and
  2. Jack R. Pladziewicz2

Published Online: 7 DEC 2011

DOI: 10.1002/9781118166123.ch10

Rate Constant Calculation for Thermal Reactions: Methods and Applications

Rate Constant Calculation for Thermal Reactions: Methods and Applications

How to Cite

Nelsen, S. F. and Pladziewicz, J. R. (2011) Intermolecular Electron Transfer Reactivity for Organic Compounds Studied Using Marcus Cross-Rate Theory, in Rate Constant Calculation for Thermal Reactions: Methods and Applications (eds H. DaCosta and M. Fan), John Wiley & Sons, Inc., Hoboken, NJ, USA. doi: 10.1002/9781118166123.ch10

Author Information

  1. 1

    Department of Chemistry, University of Wisconsin, Madison, WI, USA

  2. 2

    Department of Chemistry, University of Wisconsin, Eau Claire, WI, USA

Publication History

  1. Published Online: 7 DEC 2011
  2. Published Print: 29 DEC 2011

ISBN Information

Print ISBN: 9780470582305

Online ISBN: 9781118166123

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Keywords:

  • intermolecular electron transfer, using Marcus cross-rate;
  • pre-exponential, barriers, averaging for cross-reactions;
  • combining cross-reaction studies with modern computations

Summary

This chapter contains sections titled:

  • Introduction

  • Determination of ΔGii (fit) Values

  • Why is the Success of Cross-Rate Theory Surprising?

  • Major Factors Determining Intrinsic Reactivities of Hydrazine Couples

  • Nonhydrazine Couples

  • Comparison of ΔGii (fit) with ΔGii (self) Values

  • Estimation of Hab from Experimental Exchange Rate Constants and DFT-Computed λ

  • Comparison with Gas-Phase Reactions

  • Conclusions

  • References