Proton transport in aqueous systems occurs by making and breaking covalent bonds, a process that classical force fields cannot reproduce. Various attempts have been made to remedy this deficiency, by valence bond theory or instantaneous proton transfers, but the ability of such methods to provide a realistic picture of this fundamental process has not been fully evaluated. Here we compare an ab initio molecular dynamics (AIMD) simulation of an excess proton in water to a simulation of a classical H3O+ in TIP3P water. The energy gap upon instantaneous proton transfer from H3O+ to an acceptor water molecule is much higher in the classical simulation than in the AIMD configurations evaluated with the same classical potential. The origins of this discrepancy are identified by comparing the solvent structures around the excess proton in the two systems. One major structural difference is in the tilt angle of the water molecules that accept an hydrogen bond from H3O+. The lack of lone pairs in TIP3P produces a tilt angle that is too large and generates an unfavorable geometry after instantaneous proton transfer. This problem can be alleviated by the use of TIP5P, which gives a tilt angle much closer to the AIMD result. Another important factor that raises the energy gap is the different optimal distance in water-water vs H3O+-water H-bonds. In AIMD the acceptor is gradually polarized and takes a hydronium-like configuration even before proton transfer actually happens. Ways to remedy some of these problems in classical simulations are discussed.
Structural aspects of the topological model of the hydrogen bond in water on auto-dissociation via proton transfer
Molecular dynamics (MD) simulations were used to investigate the structure and lifetimes of hydrogen bonds and auto dissociation via proton transfer in bulk water using a reactive and dissociative all-atom potential that has previously been shown to match a variety of water properties and proton transfer. Using the topological model, each molecule's donated and accepted hydrogen bonds were labeled relative to the other hydrogen bonds on neighboring waters, providing a description of the effect of these details on the structure, dynamics and autoionization of water molecules. In agreement with prior data, asymmetric bonding at the sub-100 femtosecond timescale is observed, as well as the existence of linear, bifurcated, and dangling hydrogen bonds. The lifetime of the H-bond, 2.1 ps, is consistent with experimental data, with short time librations on the order of femtoseconds. The angular correlation functions, the presence of a second shell water entering the first shell, and OH vibrational stretch frequencies were all consistent with experiment or ab initio calculations. The simulations show short-lived (femtoseconds) dissociation of a small fraction of water molecules followed by rapid recombination. The role of the other H-bonds to the acceptor and on the donor plays an important part in proton transfer between the molecules in auto dissociation and is consistent with the role of a strong electric field caused by local (first and second shell) waters on initiating dissociation. The number of H-bonds to the donor water is 4.3 per molecule in the simulations, consistent with previous data regarding the number of hydrogen bonds required to generate this strong local electric field that enhances dissociation. The continuous lifetime autocorrelation function of the H-bond for those molecules that experience dissociation is considerably longer than that for all molecules that show no proton transfer.
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- Award ID(s):
- 1609044
- NSF-PAR ID:
- 10090791
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 20
- Issue:
- 24
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 16414 to 16427
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c8cp02592d
