An ab initio path integral molecular dynamics study of double proton transfer in the formic acid dimer

Shinichi Miura, Mark Tuckerman, Michael L. Klein

Research output: Contribution to journalArticle

Abstract

Double proton transfer in the formic acid dimer has been investigated with Car-Parrinello ab initio molecular dynamics calculations. The electronic structure of the dimer has been obtained using gradient-corrected density functional theory based on the B-LYP (Becke exchange [Phys. Rev. A 38, 3098 (1988)] and Lee-Yang-Parr correlation [Phys. Rev. B 37, 785 (1988)] functional. The optimized equilibrium and saddle-point geometries, obtained by simulated annealing, are in good agreement with previous ab initio quantum chemical predictions and experiment. Thermal and quantum fluctuations of nuclei along the double proton transfer reaction path have also been investigated at T=300K. Thermal fluctuations give a broad distribution of nuclei around the minimum energy path on the potential energy surface. Quantum fluctuations, investigated using ab initio path integral molecular dynamics, make the distribution even broader around the equilibrium structure, and cause the distribution to deviate appreciably from the minimum energy path on approaching the reaction barrier. In particular, the system passes through higher energy regions than the geometrical saddle point by tunneling; an observation which is consistent with the conventional understanding of heavy-light-heavy mass combination reactions. While there is asynchronous movement of the two protons around the equilibrium structure, synchronous movement becomes relevant on approaching the reaction barrier.

Original languageEnglish (US)
Pages (from-to)5290-5299
Number of pages10
JournalJournal of Chemical Physics
Volume109
Issue number13
DOIs
StatePublished - 1998

Fingerprint

formic acid
Proton transfer
Dimers
Molecular dynamics
dimers
molecular dynamics
Potential energy surfaces
protons
saddle points
Simulated annealing
Electronic structure
Density functional theory
Protons
Railroad cars
nuclei
Geometry
simulated annealing
energy
Experiments
potential energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

An ab initio path integral molecular dynamics study of double proton transfer in the formic acid dimer. / Miura, Shinichi; Tuckerman, Mark; Klein, Michael L.

In: Journal of Chemical Physics, Vol. 109, No. 13, 1998, p. 5290-5299.

Research output: Contribution to journalArticle

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