Competing quantum effects in the dynamics of a flexible water model

Habershon, Scott; Markland, Thomas E.; Manolopoulos, David E.

doi:doi:10.1063/1.3167790

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Numerous studies have identified large quantum mechanical effects in the dynamics of liquid water. In this paper, we suggest that these effects may have been overestimated due to the use of rigid water models and flexible models in which the intramolecular interactions were described using simple harmonic functions. To demonstrate this, we introduce a new simple point charge model for liquid water, q-TIP4P/F, in which the O–H stretches are described by Morse-type functions. We have parametrized this model to give the correct liquid structure, diffusion coefficient, and infrared absorption frequencies in quantum (path integral-based) simulations. The model also reproduces the experimental temperature variation of the liquid density and affords reasonable agreement with the experimental melting temperature of hexagonal ice at atmospheric pressure. By comparing classical and quantum simulations of the liquid, we find that quantum mechanical fluctuations increase the rates of translational diffusion and orientational relaxation in our model by a factor of around 1.15. This effect is much smaller than that observed in all previous simulations of empirical water models, which have found a quantum effect of at least 1.4 regardless of the quantum simulation method or the water model employed. The small quantum effect in our model is a result of two competing phenomena. Intermolecular zero point energy and tunneling effects destabilize the hydrogen-bonding network, leading to a less viscous liquid with a larger diffusion coefficient. However, this is offset by intramolecular zero point motion, which changes the average water monomer geometry resulting in a larger dipole moment, stronger intermolecular interactions, and a slower diffusion. We end by suggesting, on the basis of simulations of other potential energy models, that the small quantum effect we find in the diffusion coefficient is associated with the ability of our model to produce a single broad O–H stretching band in the infrared absorption spectrum.

Article Outline

INTRODUCTION
QUANTUM WATER MODELS
QUANTUM SIMULATION METHODS
1. Path integral molecular dynamics
2. Ring polymer molecular dynamics
3. Partially adiabatic centroid molecular dynamics
4. Additional computational details
VALIDATION OF THE q-TIP4P/F MODEL
1. Static equilibrium properties
2. Dynamical properties
3. Summary
COMPETING QUANTUM EFFECTS
1. Computational results
2. Analysis and discussion
CONCLUDING REMARKS

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KEYWORDS and PACS

Keywords

diffusion, hydrogen bonds, infrared spectra, liquid structure, tunnelling, water

PACS

61.25.Em

Molecular liquids
66.10.C-

Diffusion and thermal diffusion
78.30.C-

Liquids

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.3167790

PUBLICATION DATA

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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