Proper and improper hydrogen bonds in liquid water

• Published in: Journal of structural chemistry Vol. 57; no. 3; pp. 497 - 506
• Main Authors: Voloshin, V. P., Naberukhin, Yu. I.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 01.05.2016
• Subjects: Atomic; Atomic/Molecular Structure and Spectra; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Molecular; Optical and Plasma Physics; Physical Chemistry; Solid State Physics; hydrogen bond network; molecular dynamics; water structure; hydrogen bond lifetime
• ISSN: 0022-4766; 1573-8779
• DOI: 10.1134/S0022476616030112

The total lifetime distributions for hydrogen bonds in snapshots of molecular dynamics simulations of water serve as a basis to identify a class of proper hydrogen bonds. Proper bonds emerge and break up when restructuring the surrounding area of the hydrogen bond networkwhich weakly depend on the properties of this individual bond, i.e., almost randomly. Therefore, the distribution of the bond lifetimes is described by an exponential function similar to the distribution of the mean free path time in gas. It is shown that proper hydrogen bonds are strong, long-lived, and tetrahedrally oriented bonds. They account for about 80% of the bonds in each snapshot. Thus, these bonds form the basis or framework of the hydrogen bond network of water. The other, improper bonds have a substantially shorter lifetime; these are weak, bifurcated, and quickly switching bonds.