Different Ways of Hydrogen Bonding in Water - Why Does Warm Water Freeze Faster than Cold Water?

Abstract

The properties of liquid water are intimately related to the H-bond network among the individual water molecules. Utilizing vibrational spectroscopy and modeling water with DFT-optimized water clusters (6-mers and 50-mers), 16 out of a possible 36 different types of H-bonds are identified and ordered according to their intrinsic strength. The strongest H-bonds are obtained as a result of a concerted push-pull effect of four peripheral water molecules, which polarize the electron density in a way that supports charge transfer and partial covalent character of the targeted H-bond. For water molecules with tetra- and pentacoordinated O atoms, H-bonding is often associated with a geometrically unfavorable positioning of the acceptor lone pair and donor σ*(OH) orbitals so that electrostatic rather than covalent interactions increasingly dominate H-bonding. There is a striking linear dependence between the intrinsic strength of H-bonding as measured by the local H-bond stretching force constant and the delocalization energy associated with charge transfer. Molecular dynamics simulations for 1000-mers reveal that with increasing temperature weak, preferentially electrostatic H-bonds are broken, whereas the number of strong H-bonds increases. An explanation for the question why warm water freezes faster than cold water is given on a molecular basis.

DOI: 10.1021/acs.jctc.6b00735

Cite this paper

@article{Tao2017DifferentWO, title={Different Ways of Hydrogen Bonding in Water - Why Does Warm Water Freeze Faster than Cold Water?}, author={Yunwen Tao and Wenli Zou and Junteng Jia and Wei Li and Dieter Cremer}, journal={Journal of chemical theory and computation}, year={2017}, volume={13 1}, pages={55-76} }