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Title: Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

Abstract

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381°C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. As a result, using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.

Authors:
 [1];  [2];  [2];  [2]
+ Show Author Affiliations
  1. Benedictine Univ., Lisle, IL (United States)
  2. Notre Dame Radiation Lab., Notre Dame, IN (United States)
Publication Date:
Research Org.:
University of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1389785
Grant/Contract Number:  
FC02-04ER15533
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical physics; Physical chemistry

Citation Formats

Marin, Timothy W., Janik, Ireneusz, Bartels, David M., and Chipman, Daniel M. Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water. United States: N. p., 2017. Web. doi:10.1038/ncomms15435.
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Marin, Timothy W., Janik, Ireneusz, Bartels, David M., & Chipman, Daniel M. Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water. United States. https://doi.org/10.1038/ncomms15435
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Marin, Timothy W., Janik, Ireneusz, Bartels, David M., and Chipman, Daniel M. Wed . "Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water". United States. https://doi.org/10.1038/ncomms15435. https://www.osti.gov/servlets/purl/1389785.
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@article{osti_1389785,
title = {Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water},
author = {Marin, Timothy W. and Janik, Ireneusz and Bartels, David M. and Chipman, Daniel M.},
abstractNote = {The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381°C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. As a result, using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.},
doi = {10.1038/ncomms15435},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Wed May 17 00:00:00 EDT 2017},
month = {Wed May 17 00:00:00 EDT 2017}
}
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https://doi.org/10.1038/ncomms15435
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  • Chipman, Daniel M.
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Theoretical characterization of temperature and density dependence of liquid water electronic excitation energy: Comparison with recent experimental data
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  • D’Abramo, Marco; Di Nola, Alfredo; Aschi, Massimiliano
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Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy
journal, February 2009

  • Elles, Christopher G.; Rivera, Christopher A.; Zhang, Yuyuan
  • The Journal of Chemical Physics, Vol. 130, Issue 8
  • DOI: 10.1063/1.3078336

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  • Proceedings of the National Academy of Sciences, Vol. 97, Issue 12
  • DOI: 10.1073/pnas.110572097

Excited state properties of liquid water
journal, December 2008

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