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Spectroscopic probing of local hydrogen-bonding structures in liquid water

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S Myneni1,2, Y Luo3,4, L Å Näslund5, M Cavalleri3, L Ojamäe6, H Ogasawara5,9, A Pelmenschikov3, Ph Wernet7, P Väterlein5, C Heske8, Z Hussain8, L G M Pettersson3 and A Nilsson5,7

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LETTER TO THE EDITOR

We have studied the electronic structure of liquid water using x-ray absorption spectroscopy at the oxygen K edge. Since the x-ray absorption process takes less than a femtosecond, it allows probing of the molecular orbital structure of frozen, local geometries of water molecules at a timescale that has not previously been accessible. Our results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms, resulting in a pronounced pre-edge feature below the main absorption edge in the spectrum. Theoretical calculations of these spectra suggest that this feature originates from specific configurations of water, for which the H-bond is broken on the H-donating site of the water molecule. This study provides a fingerprint for identifying broken donating H-bonds in the liquid and shows that an unsaturated H-bonding environment exists for a dominating fraction of the water molecules.


PACS

61.25.Em Molecular liquids

78.70.Dm X-ray absorption spectra

Subjects

Soft matter, liquids and polymers

Condensed matter: electrical, magnetic and optical

Dates

Issue 8 (4 March 2002)

Received 15 January 2002

Published 15 February 2002



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