# Instantaneous Normal Mode Analysis of Supercooled Water

## Abstract

We use the instantaneous normal mode approach to provide a description of the local curvature of the potential energy surface of a model for water. We focus on the region of the phase diagram in which the dynamics may be described by the mode-coupling theory. We find, surprisingly, that the diffusion constant depends mainly on the fraction of directions in configuration space connecting different local minima, supporting the conjecture that the dynamics are controlled by the geometric properties of configuration space. Furthermore, we find an unexpected relation between the number of basins accessed in equilibrium and the connectivity between them.

The study of the dynamics in supercooled liquids has received great interest in recent years due to possibilities opened by novel experimental techniques , detailed theoretical predictions , and by the possibility of following the microscopic dynamics via computer simulation . One important theoretical approach developed recently is the ideal mode coupling theory(MCT) , which quantitatively predicts the time evolution of correlation functions and the dependence on temperature $`T`$ of characteristic correlation times. Unfortunately, the temperature region in which MCT is able to make predictions for the long time dynamics is limited to weakly supercooled states . In parallel with the development of MCT, theoretical work  has called attention to thermodynamic approaches to the glass transition, and to the role of configurational entropy in the slowing down of dynamics. These theories, which build on ideas put forward some time ago , stress the relevance of the topology of the potential energy surface (PES) explored in supercooled states. Detailed studies of the PES may provide insights on the slow dynamics of liquids, and new ideas for extending the present theories to the deep supercooling regime.

The instantaneous normal mode (INM) approach uses the eigenvectors (normal modes) and eigenvalues of the Hessian matrix (the second derivative of the potential energy) to provide an “instantaneous” representation of the PES in the neighborhood of an equilibrium phase space point. Examples of INM analysis have appeared for a few representative liquids . In this Letter we present INM calculations for a rigid water molecule model, the SPC/E potential , for several temperatures and densities in supercooled states. The reasons for selecting such a system are twofold: (i) The SPC/E model has been studied in detail, and it has been shown that its dynamics follows closely the predictions of MCT . Furthermore, the ($`\rho `$, $`T`$) dependence of the configurational entropy has been calculated, and shown to correlate with the dynamical behavior . (ii) The SPC/E model has a maximum of the diffusion constant $`D`$ under pressure along isotherms, as observed experimentally . The maxima in $`D`$ can be used as sensitive probes for testing proposed relations between the change in topology of configuration space and the change in $`D`$.

We analyze recent simulations  for six densities between $`0.95`$ and $`1.3`$ g/cm<sup>3</sup> and five temperatures for each density. For each state point, we extract 100 equally-spaced configurations , from which we calculate and diagonalize the Hessian using the center of mass and the three principal inertia momenta vectors as molecular coordinates . For each configuration, we classify the imaginary modes into two categories: (i) shoulder modes and (ii) double-well modes, according to the shape of the PES along the corresponding eigenvector . The shoulder modes are modes for which the negative curvature appears as a result of a local anharmonicity; the double-well modes include only the directions in configuration space which connect two adjacent minima. The classification of the modes is done by studying the shape of the PES along the eigenvector corresponding to the mode, i.e. beyond the point in configuration space where such modes have been calculated. In this respect, the potential energy along the eigenvector direction may be different from the actual curvilinear direction described by the time evolution of the eigenvector under consideration. Furthermore, some modes classified as double-well may be related to intra-basin motions  and therefore may not be relevant to describe diffusivity. In the present study we show — using the $`D`$ maxima line as a guide — that these spurious features are negligible.

Fig. 1 shows the density dependence of the fractions of imaginary (unstable) modes $`f_u`$, double-well modes $`f_{dw}`$, and of shoulder modes $`f_{sh}`$, where $`f_u=f_{dw}+f_{sh}`$; we also show $`D`$ for the same state points. The close correlation of $`f_{dw}`$ and $`D`$ is striking. At $`\rho 1.15`$ g/cm<sup>3</sup>, $`D`$ has a maximum; at this $`\rho `$, the increase of diffusion constant caused by the the progressive disruption of the hydrogen bond network on increasing the density is balanced by slowing down of the dynamics due to increased packing. At the same density, $`f_u`$ and $`f_{dw}`$ also show maxima, supporting the view that these quantities are a good indicator of the molecular mobility. There is also a weak maximum in $`f_{sh}`$, but at a $`\rho <1.15`$ g/cm<sup>3</sup>. The presence of maxima in both $`D`$ and $`f_{dw}`$ at the same density suggests that, for the SPC/E potential, $`f_{dw}`$ is directly related to $`D`$. The relation between $`D`$ and $`f_{dw}`$ is shown in Fig. 2 for all the studied isochores. We note that $`D`$ in this system is a monotonic function of $`f_{dw}`$ and that all points fall on the same master curve, notwithstanding the large range of $`D`$ values analysed. Thus, surprisingly, in SPC/E water, the knowledge of the fraction of directions in configuration space leading to a different basin, $`f_{dw}`$, is sufficient to determine the value of $`D`$. We also note from Fig. 2 that $`D`$ vanishes, but at a small non-zero value of $`f_{dw}0.007`$ (vertical arrow) , suggesting that indeed a small number of spurious double-well modes, related to intrabasin motion , are still included in our classification.

The reduction of mobility on cooling in the studied $`(\rho ,T)`$ range – where MCT provides a description of the dynamics – appears related to the geometrical properties of the PES, i.e. the system mobility is reduced because the number of directions connecting different local minima (needed to explore freely the configuration space) is decreasing . Hence, the observed reduced mobility is mainly related to the geometry of the PES, i.e. it is “entropic” in origin.

MCT seems to be able to describe the entropic slowing down of the dynamics associated with the vanishing of $`f_{dw}`$. This is consistent with the general consensus that the missing decay channels for the correlations responsible for the failure of MCT at very low $`T`$ are activated processes. To make closer contact with MCT, we compare in Fig. 3 the density dependence of the MCT critical temperature $`T_{MCT}`$  with the $`T`$ at which the fraction of double-well modes goes to zero, as well as with the $`T`$ at which $`f_{dw}`$ reaches the estimated asymptotic value of $`0.007`$ , to take into account the small over counting intrinsic in the mode classification. We observe that the $`f_{dw}=0`$ locus tracks closely the $`T_{MCT}`$ line, but that the $`f_{dw}=0.007`$ locus nearly coincides with the $`T_{MCT}`$ line.

The results presented here suggest that the liquid dynamics in the MCT region of SPC/E water is controlled by the average connectivity in configuration space. On the other hand, for the same model, the ($`\rho `$, $`T`$) dependence of the configurational entropy $`S_{\text{conf}}`$ – which, in the Stillinger-Weber  formalism, can be defined as the logarithm of the number of different basins $`\mathrm{\Omega }`$ in configuration space – has also been calculated and shown to correlate with $`D`$. Since no a priori relation is expected between the connectivity of the local minima and their number, we consider particularly interesting the observation of such a relation. For this reason, we show in Fig. 4 a “parametric plot” (in the parameter $`D`$) of $`f_{dw}`$ versus $`S_{\text{conf}}`$ for all studied densities. Fig. 4 shows a linear relation between $`\mathrm{ln}(f_{dw})`$ and $`S_{\text{conf}}`$, i.e. between $`f_{dw}`$ and the number of basins (since $`\mathrm{\Omega }=\mathrm{exp}(S_{\text{conf}}/k_B)`$) and highlight the existence of an unexpected relation between the number of basins accessed in equilibrium and the connectivity between them. This novel feature of the PES contributes to a better understanding of the water dynamics, and may contribute to the understanding of the dynamics of glass-forming liquids.

We thank T. Keyes for useful discussions, and the NSF for support; FS acknowledges partial support from MURST (PRIN 98).