The hydrogen bond in ice probed by soft x-ray spectroscopy and density functional theory

Journal Article · Fri Apr 15 04:00:00 EDT 2005 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.1879752· OSTI ID:20722239

Nilsson, A; Ogasawara, H; Cavalleri, M; Nordlund, D; Nyberg, M; Wernet, Ph; Pettersson, L G.M. ^[1]

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1. Stanford Synchrotron Radiation Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025 (United States)

We combine photoelectron and x-ray absorption spectroscopy with density functional theory to derive a molecular orbital picture of the hydrogen bond in ice. We find that the hydrogen bond involves donation and back-donation of charge between the oxygen lone pair and the O-H antibonding orbitals on neighboring molecules. Together with internal s-p rehybridization this minimizes the repulsive charge overlap of the connecting oxygen and hydrogen atoms, which is essential for a strong attractive electrostatic interaction. Our joint experimental and theoretical results demonstrate that an electrostatic model based on only charge induction from the surrounding medium fails to properly describe the internal charge redistributions upon hydrogen bonding.

• OSTI ID: 20722239
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 15 Vol. 122; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTROSCOPY
CHEMICAL BONDS
DENSITY FUNCTIONAL METHOD
HYDROGEN
ICE
INTERACTIONS
MOLECULAR ORBITAL METHOD
OXYGEN
PHOTOELECTRON SPECTROSCOPY
SOFT X RADIATION
X-RAY SPECTRA
X-RAY SPECTROSCOPY