# Slow dynamics of water under pressure

## Abstract

We perform lengthy molecular dynamics simulations of the SPC/E model of water to investigate the dynamics under pressure at many temperatures and compare with experimental measurements. We calculate the isochrones of the diffusion constant $`D`$ and observe power-law behavior of $`D`$ on lowering temperature with an apparent singularity at a temperature $`T_c(P)`$, as observed for water. Additional calculations show that the dynamics of the SPC/E model are consistent with slowing down due to the transient caging of molecules, as described by the mode-coupling theory (MCT). This supports the hypothesis that the apparent divergences of dynamic quantities along $`T_c(P)`$ in water may be associated with “slowing down” as described by MCT.

On supercooling water at atmospheric pressure, many thermodynamic and dynamic quantities show power-law growth . This power law behavior also appears under pressure, which allows measurement of the locus of apparent power-law singularities in water \[Fig. 1(a)\]. The possible explanations of this behavior have generated a great deal of interest. In particular, three scenarios have been considered: (i) the existence of a spinodal bounding the stability of the liquid in the superheated, stretched, and supercooled states ; (ii) the existence of a liquid-liquid transition line between two liquid phases differing in density ; (iii) a singularity-free scenario in which the thermodynamic anomalies are related to the presence of low-density and low-entropy structural heterogeneities . Based on both experiments  and recent simulations , several authors have suggested that the power-law behavior of dynamic quantities might be explained by the transient caging of molecules by neighboring molecules, as described by the mode-coupling theory (MCT) , which we address here. This explanation would indicate that the dynamics of water are explainable in the same framework developed for other fragile liquids , at least for temperatures above the homogeneous nucleation temperature $`T_H`$. Moreover, this explanation of the dynamic behavior on supercooling may be independent of the above scenarios suggested for thermodynamic behavior \[Fig. 1(a)\].

Here we focus on the behavior of the diffusion constant $`D`$ under pressure, which has been studied experimentally . We perform molecular dynamics simulations in the temperature range 210 K – 350 K for densities ranging from 0.95 g/cm<sup>3</sup> – 1.40 g/cm<sup>3</sup> \[Table I\] using the extended simple point charge potential (SPC/E) . We select the SPC/E potential because it has been previously shown to display power-law behavior of dynamic quantities, as observed in supercooled water at ambient pressure .

In Fig. 2, we compare the behavior of $`D`$ under pressure at several temperatures for our simulations and the

experiments of ref. . The anomalous increase in $`D`$ is qualitatively reproduced by SPC/E, but the quantitative increase of $`D`$ is significantly larger than that observed experimentally. This discrepancy may arise form the fact that the SPC/E potential is under-structured relative to water , so applying pressure allows for more bond breaking and thus greater diffusivity than observed experimentally. We also find that the pressure where $`D`$ begins to decrease with pressure – normal behavior for a liquid – is larger than that observed experimentally. This simple comparison of $`D`$ leads us to expect that the qualitative dynamic features we observe in the SPC/E potential will aid in the understanding of the dynamics of water under pressure, but will likely not be quantitatively accurate.

We next determine the approximate form of the lines of constant $`D`$ (isochrones) by interpolating our data over the region of the phase diagram studied \[Fig. 1(b)\]. We note that the locus of points where the slope of the isochrones changes sign (i.e. the locus of points where $`D`$ obtains a maximum value) is close to the $`T_{\text{MD}}`$ locus . At each density studied, we fit $`D`$ to a power law $`D(T/T_c1)^\gamma `$. The shape of the locus of $`T_c`$ values compares well with that observed experimentally , and changes slope at the same pressure \[Figs. 1(a) and (b)\]. We find the striking feature that $`\gamma `$ decreases under pressure for the SPC/E model, while $`\gamma `$ increases experimentally \[Fig. 3\]. This disagreement underscores the need to improve the dynamic properties of water models, most of which already provide an adequate account of static properties .

We next consider interpretation of our results using MCT, which has been used to quantitatively describe the weak supercooling regime – i.e., the temperature range where the characteristic times become three or

four orders of magnitude larger than those of the normal liquid . The region where experimental data are available in supercooled water is exactly the region where MCT holds. MCT provides a theoretical framework in which the slowing down of the dynamics arises from caging effects, related to the coupling between density modes, mainly over length scales on the order of the nearest neighbors. In this respect, MCT does not require the presence of a thermodynamic instability to explain the power-law behavior of the characteristic times.

MCT predicts power-law behavior of $`D`$, and also that the Fourier transform of the density-density correlation function $`F(q,t)`$, typically referred to as the intermediate scattering function, decays via a two-step process. $`F(q,t)`$ can be measured by neutron scattering experiments and is calculated via

$$F(q,t)\frac{1}{S(q)}\underset{j,k=1}{\overset{N}{}}e^{i𝐪[𝐫_k(t)𝐫_j(0)]},$$
(1)   
where $`S(q)`$ is the structure factor . In the first relaxation step, $`F(q,t)`$ approaches a plateau value $`F_{\text{plateau}}(q)`$; the decay from the plateau has the form $`F_{\text{plateau}}(q)F(q,t)t^b`$, where $`b`$ is known as the von Schweidler exponent. According to MCT, the value $`b`$ is completely determined by the value of $`\gamma `$ , so calculation of these exponents for SPC/E determines if MCT is consistent with our results.

The range of validity of the power-law $`t^b`$ is strongly $`q`$-dependent , making unambiguous calculation of $`b`$ difficult. Fortunately, the same exponent $`b`$ controls the long-time behavior of $`F(q,t)`$ at large $`q`$. Indeed, MCT predicts that at long time, $`F(q,t)`$ decays according to a Kohlrausch-Williams-Watts stretched exponential

$$F(q,t)=A(q)\mathrm{exp}\left[\left(\frac{t}{\tau (q)}\right)^{\beta (q)}\right],$$
(2)   
with $`lim_q\mathrm{}\beta (q)=b`$ . We show the $`q`$-dependence of $`\beta `$ for each density studied at $`T=210`$ K \[Fig. 4\]. We also calculate $`\beta `$ for the “self-part” of $`F(q,t)`$, denoted $`F_{\text{self}}(q,t)`$ . In addition, we show the expected value of $`b`$ according to MCT, using the values of $`\gamma `$ extrapolated from Fig. 3. The large-$`q`$ limit of $`\beta `$ appears to approach the value predicted by MCT . Hence we conclude that the dynamic behavior of the SPC/E potential in the pressure range we study is consistent with slowing down as described by MCT \[Fig. 5\]. We also note that on increasing pressure, the values of the exponents become closer to those for hard-sphere ($`\gamma =2.58`$ and $`b=0.545`$) and Lennard-Jones ($`\gamma =2.37`$ and $`b=0.617`$) systems . This confirms that the hydrogen-bond network

is destroyed under pressure and that the water dynamics become closer to that of normal liquids, where core repulsion is the dominant mechanism.

A significant result of our analysis is the demonstration that MCT is able to rationalize the dynamic behavior of the SPC/E model of water at all pressures. In doing so, MCT encompasses both the behavior at low pressures, where the mobility is essentially controlled by the presence of strong energetic cages of hydrogen bonds, and at high pressures, where the dynamics are dominated by excluded volume effects.

We wish to thank A. Rinaldi, S. Sastry, and A. Scala for their assistance. FWS is supported by an NSF graduate fellowship. The Center for Polymer Studies is supported by NSF grant CH9728854 and British Petroleum.