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Smith JD, Cappa CD, Messer BM, et al. Probing the local structure of liquid water by X-ray absorption spectroscopy. J Phys Chem B. 2006;110(40):20038-45doi: 10.1021/jp063661c.
Smith, J. D., Cappa, C. D., Messer, B. M., Drisdell, W. S., Cohen, R. C., & Saykally, R. J. (2006). Probing the local structure of liquid water by X-ray absorption spectroscopy. The journal of physical chemistry. B, 110(40), 20038-45. https://doi.org/10.1021/jp063661c
Smith, Jared D, et al. "Probing the local structure of liquid water by X-ray absorption spectroscopy." The journal of physical chemistry. B vol. 110,40 (2006): 20038-45. doi: https://doi.org/10.1021/jp063661c
Smith JD, Cappa CD, Messer BM, Drisdell WS, Cohen RC, Saykally RJ. Probing the local structure of liquid water by X-ray absorption spectroscopy. J Phys Chem B. 2006 Oct 12;110(40):20038-45. doi: 10.1021/jp063661c. PMID: 17020392.
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J Phys Chem B. 2006 Oct 12;110(40):20038-45. doi: 10.1021/jp063661c.

Probing the local structure of liquid water by X-ray absorption spectroscopy.

The journal of physical chemistry. B

Jared D Smith, Christopher D Cappa, Benjamin M Messer, Walter S Drisdell, Ronald C Cohen, Richard J Saykally

Affiliations

  1. Department of Chemistry, University of California, Berkeley, California 94721, USA.

PMID: 17020392 DOI: 10.1021/jp063661c

Abstract

It was recently suggested that liquid water primarily comprises hydrogen-bonded rings and chains, as opposed to the traditionally accepted locally tetrahedral structure (Wernet et al. Science 2004, 304, 995). This controversial conclusion was primarily based on comparison between experimental and calculated X-ray absorption spectra (XAS) using computer-generated ice-like 11-molecule clusters. Here we present calculations which conclusively show that when hydrogen-bonding configurations are chosen randomly, the calculated XAS does not reproduce the experimental XAS regardless of the bonding model employed (i.e., rings and chains vs tetrahedral). Furthermore, we also present an analysis of a recently introduced asymmetric water potential (Soper, A. K. J. Phys.: Condens. Matter 2005, 17, S3273), which is representative of the rings and chains structure, and make comparisons with the standard SPC/E potential, which represents the locally tetrahedral structure. We find that the calculated XAS from both potentials is inconsistent with the experimental XAS. However, we also show the calculated electric field distribution from the rings and chains structure is strongly bimodal and highly inconsistent with the experimental Raman spectrum, thus casting serious doubt on the validity of the rings and chains model for liquid water.

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