Theoretical Studies of Proton Transfer Reactions - Energy Barriers and the Marcus Equation

Chih Hung Chu, Jia-Jen Ho

Research output: Contribution to journalArticle

Abstract

The reactants, ion-dipole complexes, transition states, and products for the proton transfer reactions HBCOH+ + OCXH → HBCO + +HOCXH optimized at the SCF/4-31G* level of theory for B, X = F, Cl, H, CH3, CH2Cl, CHCl2 and CCl3 are studied. The intrinsic barrier ΔE#BX correlates with the degree of the O-O bond contraction in the transition structure. Both intrinsic and overall barriers can be predicted with the aid of Marcus theory. Progressive degrees of chlorination of the alkyl group in B produce decreases in the barrier to proton transfer from HBCOH+ to OCXH and increases in the reverse transfer barriers. These changes can be quantitatively reproduced by the Marcus equation for all systems.

Original languageEnglish
Pages (from-to)455-462
Number of pages8
JournalJournal of the Chinese Chemical Society
Volume44
Issue number5
DOIs
Publication statusPublished - 1997 Jan 1

Keywords

  • Ab initio
  • Marcus theory
  • Proton-transfer barriers
  • Protonated formaldehyde dimer derivatives

ASJC Scopus subject areas

  • Chemistry(all)

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