Quantum Dynamics of an Excess Proton in Water Using an Extended Empirical Valence-Bond Hamiltonian

The classical and quantum dynamics of an excess proton in water is studied by molecular dynamics simulations. The electronic structure of the system is described by an extended multistate valence-bond Hamiltonian that allows for the breaking and formation of O−H+ bonds. The proton quantum character...

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Bibliographic Details
Published in:The journal of physical chemistry. B 1998-05, Vol.102 (22), p.4261-4264
Main Authors: Vuilleumier, Rodolphe, Borgis, Daniel
Format: Article
Language:English
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Summary:The classical and quantum dynamics of an excess proton in water is studied by molecular dynamics simulations. The electronic structure of the system is described by an extended multistate valence-bond Hamiltonian that allows for the breaking and formation of O−H+ bonds. The proton quantum character is treated by means of an effective (path-integral) proton-transfer surface. Whereas classical simulations predict that the hydrated proton appears in a mixture of and structures, inclusion of proton quantization leads to the prevalence of . The proton-transfer mechanism can be described mostly as the translocation of a transient structure across the water hydrogen-bond network. The computed lifetime of a particular is close to 2 ps, a value compatible with experimental estimates.
ISSN:1520-6106
1520-5207
DOI:10.1021/jp9807423