title: 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.
authors.affiliation: Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University , 3215 Daniel Avenue, Dallas, Texas 75275-0314, United States.
authors.forename: Yunwen
authors.initials: Y
authors.lastname: Tao
authors.affiliation: Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University , 3215 Daniel Avenue, Dallas, Texas 75275-0314, United States.
authors.forename: Wenli
authors.initials: W
authors.lastname: Zou
authors.affiliation: Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, P. R. China.
authors.forename: Junteng
authors.initials: J
authors.lastname: Jia
authors.affiliation: Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, P. R. China.
authors.forename: Wei
authors.initials: W
authors.lastname: Li
authors.affiliation: Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University , 3215 Daniel Avenue, Dallas, Texas 75275-0314, United States.
authors.forename: Dieter
authors.identifier: 0000-0002-6213-5555
authors.initials: D
authors.lastname: Cremer