Distinguishing Weak and Strong Hydrogen Bonds in Liquid Water-A Potential of Mean Force-Based Approach

The ability to form hydrogen bonds is one of the most important factors behind water's many anomalous properties. However, there is still no consensus on the hydrogen bond structure of liquid water, including the average number of hydrogen bonds in liquid water. We use molecular dynamics simulations of the polarizable iAMOEBA water model for investigating the hydrogen bond characteristics of liquid water over a wide range of temperatures and pressures. Geometric definitions of a hydrogen bond often use a rectangular region on the plane of hydrogen bond distances and angles. In this work, we find that an elliptical region is more appropriate for the identification of hydrogen bonds, based on statistically favorable molecular configurations. The two-dimensional potential of mean force (PMF) landscape along the hydrogen bond distance (O-H) and angle (O-H-O) is calculated for identifying the statistically favored molecular configurations, which is then used for defining hydrogen bond formation as well as the strength of a hydrogen bond. We further propose a new approach to characterize the hydrogen bonds as strong when the PMF is lower than -2 kT. Using this definition, a consistent explanation for the different average numbers of hydrogen bonds in water is obtained in agreement with the literature. Simulations are also performed with the rigid and nonpolarizable TIP4P/2005 water model. Both water models are qualitatively consistent in predicting the distribution of double-, single-, and non-donor configurations, in line with experimental data, while the iAMOEBA water model yields more quantitatively precise results, including a 10-15% double-donor fraction at 90 °C and 1 atm. The method is also demonstrated to be applicable to the recent, and more general, three-dimensional PMF-based definition of hydrogen bonds.