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Theoretical Studies of Proton Transfer Reactions—Energy Barriers and the Marcus Equation
Author(s) -
Chu ChihHung,
Ho JiaJen
Publication year - 1997
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199700070
Subject(s) - chemistry , marcus theory , proton , transition state , dipole , transfer (computing) , transition state theory , computational chemistry , ion , thermodynamics , reaction rate constant , kinetics , organic chemistry , catalysis , physics , quantum mechanics , parallel computing , computer science
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, CH 3 , CH 2 Cl, CHCl 2 and CCl 3 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.