Hydrogen Bonding and OH-Stretch Spectroscopy in Water: Hexamer (Cage), Liquid Surface, Liquid, and Ice.
We present a unified picture of how OH-stretch spectroscopy in water can be understood in terms of hydrogen bonding for the four systems listed in the title. To understand the strength, and hence OH-stretch frequency, of a hydrogen bond, it is crucial to consider the number of additional acceptor hydrogen bonds made by both the donor and acceptor molecules. This necessity for focusing on the hydrogen-bond environment of both donor and acceptor molecules follows from quantum chemical considerations and is related to the three-body interactions in water. Armed with this understanding we can make a detailed interpretation of the OH-stretch IR absorption spectrum of the cage conformer for HOD(D2O)5 and the imaginary part of the ssp OH-stretch sum-frequency spectrum of the surface of liquid D2O with dilute HOD.
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, United States.
C J
CJ
Tainter
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, United States.
Y
Y
Ni
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, United States.
L
L
Shi
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, United States.
J L
JL
Skinner
absorption; donor−acceptor pairs; sum-frequency generation