Theoretical Studies of Quantum Water

David Ratcliffe Department of Physics, University of York, York, YO10 5DD, UK

Summary

Method

Water exhibits an unusual temperature of maximum density, which we suggest may be the result of the cage structures of hexagonal ice not all breaking down immediately after the phase transition. Molecular dynamics simulations on water were ran at various temperatures from 273K to 1500K. The system exhibited extreme hysteresis and despite attempts to reduce this by increasing system size the melting point proved elusive. Attempts to locate the cage structures that would only be present just above the melting point were inconclusive as this area was inaccessible. Runs at temperatures where they should not be present did indeed show they were absent. Investigations into the hydrogen bonding network showed that these bonds become weaker at higher temperatures and were transient in nature, with a given hydrogen changing which oyxgen it was hydrogen bonded to numerous times throughout each simulation. The oxygen-hydrogen bonds, however, are unchanging in strength and the pair of atoms involved in each do not change over the course of a run.

The water monomer, consisting of two hydrogen atoms bonded to a single oxygen atom, was modelled.
Multiple settings were varied to see which gave the best match with the experimental oxygen-hydrogen bond length and the hydrogen-oxygen-hydrogen bond angle of 0.9572 and 104.52 o respectively.

Bond length did not vary significantly with any settings, but the angle did as shown in the above graphs. A cut off energy of 380eV, ultrasoft pseudopotential, a unit cell of 8x8x8, and a GGA exchange-correlation functional were chosen. With this single molecule system set up molecular dynamics simulations in the NVE ensemble were run at various time steps. This is the constant volume and energy ensemble. The time step used for future runs is determined by seeing which of these runs do not have an energy drift over 500 steps.

Introduction

Water is an unusual substance with many anomalous properties. The temperature of maximum density lying at 4 oC is one of these. While the density of most substances increases with decreasing temperature, water not only contracts on melting but also continues to increase in density when heated to just above it's melting point. The expansion on freezing is due to the poor packing efficiency of the ice unit cell. This consists of 8 molecules forming a hexameric box, and is large enough to contain interstitial water molecules [1]. We theorise that upon melting, some of these cage structures survive, and that as temperature is increased further free water molecules can be forced inside of them, increasing density. The temperature of maximum density would then be due to the effects of increased thermal motion working to decrease the density overcoming this caging effect when the temperature reached 4 oC. CASTEP was used to run ab initio molecular dynamics simulations of water at a range of temperatures to try and identify these cages.

A time step of 0.6fs was chosen and used for all future runs. Runs on a 16 molecule system were started in the NVT ensemble, which is the ensemble for constant volume and temperature. Single temperature runs over 3000 time steps were done for temperatures from 273K to 1500K to see if the system would melt, and those above 800K did. The unusually high melting temperature is due to hysteresis from the superheating for the solid system. This was investigated by running NVT runs along the lengths of the cooling at heating parts of the hysteresis curve, from 50K to 800K in steps of 150K, with 3000 time steps at each temperature. As the hysteresis was large the process was repeated for a 32 molecule system. This still produced an unworkably large hysteresis loop. With the melting point inaccessible the 32 molecule system was instead simulated at temperatures from 500K to 700K on the cooling part of the hysteresis curve in the hopes of seeing some variation over the range of temperatures.

Results

The hysteresis effect was significant for both the 16 and 32 molecule systems, and as such accurate calculations for the melting point could not be made.

The heaxgonal ice basic structure [2]

CASTEP, Density Functional Theory and Molecular Dynamics

CASTEP was used to run molecular dynamics simulations on water. Molecular dynamics is the process of calculating the trajectories of each atom in a system by solving Newton's equation of motion, allowing the system to evolve for a short time step, and then recalculating these trajectories. Doing this over many time steps allows the evolution of the system with time to be seen.

Some clustering was observed in the 900K single temperature run, but this does not seem to be a cage structure. No other runs showed any indication of cages being present. The runs along the cooling part of the hysteresis curve were analysed by counting the number of O-H and hydrogen bonds present every 1000 time steps to determine if the network was static or if the bonds were transient. The results are shown in the table below.

To calculate the trajectories the forces must be known, and CASTEP uses density functional theory to determine these interactions. By treating the large, relatively slow moving nuclei as classical particles, the interactions can be considered by looking at only the electrons. DFT uses the fact that the ground state energy and density of electrons is exactly the same as that of non-interacting particles in a spatially modified potential [3]. The Schroedinger equation for non-interacting particles is:

The density functional can be determined by known classical-like results and an approximation for the quantum mechanical effects in the form of the exchange functional. By making the systems examined periodic the wavefunction can be simplified using Bloch's theorem and expressed as an infinite series of plane waves of the form:

Conclusions
No evidence of cage structures was found in any of these runs. This is not unexpected as they should only be present just above the melting point, and due to the extreme hysteresis this temperature was impossible to determine accurately, so no runs in this region were possible. Hydrogen bonding is weaker in the higher temperature systems. This agrees with theory [4], as they should weaken as their length increases, which is the case at higher temperatures due to increased thermal motion.

The coefficient CG becomes small as G increases, corresponding to an increase in kinetic energy. As such the series can be truncated at a chosen cut off energy where further terms become negligibly small [3]. With an expression of the wavefunction of the electrons determined the variational principle can be used to find the ground state. The contributions of the core can be given by treating the nucleus and inner electrons as a single ion and replacing the nuclear potential with an ionic pseudopotential.

There does seem to be a trend for fewer hydrogen bonds in higher temperature systems on the cooling part of the hysteresis curve. However, a lack of data points for the upper end of these calculations make this difficult to comment definitively on.

References
[1] A. H. Narten, M. D. Danford and H. A. Levy. X-Ray diffraction study of liquid water in the temperature range 4-200 C. Faraday Discuss. 43 (1967) 97-107. [2] M. Chaplin. Hexagonal Ice [Online] London South Bank University. Available at: http://www.lsbu.ac.uk/water/ice1h.html [Accessed 22nd May 2013] [3] P. Hasnip. Introduction to first-principles modelling and CASTEP [Online] Department of Physics, University of York. Available at: http://www-users.york.ac.uk/~pjh503/DFT/intro_DFT_CASTEP.pdf [Accessed 21 st May 2013] [4] X. Li, B. Walker, A. Michaelides. Quantum nature of the hydrogen bond. PNAS 108 (2011) 63696373

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