Electrochemical bond-breaking reactions: A comparison of large scale simulation results with analytical theory

A. Calhoun, M.T.M. Koper, G.A. Voth

Research output: Contribution to journalArticleAcademicpeer-review

41 Citations (Scopus)
3 Downloads (Pure)

Abstract

The adiabatic free energy surface for the electrochemically induced dissociation of a methyl halide MeX (MeX + e- ¿ Me + X-) is computed from molecular dynamics (MD) simulations based on an underlying Hamiltonian developed to describe such processes. A two-dimensional free energy surface as a function of a collective solvent coordinate and the intramolecular Me-X bond length is computed. The theoretical basis of the simulations is a novel extension of the Anderson-Newns Hamiltonian to describe the coupling of the electron transfer to the bond-breaking process. A comparison of the simulation results is made with the standard analytical theory which is developed by virtue of several simplifying assumptions. It is found that the nonlinear microscopic features of the system produce significant deviations from the predictions of the analytical model.
Original languageEnglish
Pages (from-to)3442-3448
JournalJournal of Physical Chemistry B
Volume103
Issue number17
DOIs
Publication statusPublished - 1999

Fingerprint Dive into the research topics of 'Electrochemical bond-breaking reactions: A comparison of large scale simulation results with analytical theory'. Together they form a unique fingerprint.

Cite this