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Title: X-ray absorption signatures of hydrogen-bond structure in water-alcohol solutions

Journal Article · · International Journal of Quantum Chemistry
DOI: https://doi.org/10.1002/qua.25802 · OSTI ID:1566411
 [1];  [2]; ORCiD logo [1]
  1. University of Washington, Seattle, WA (United States)
  2. University of Washington, Pullman, WA (United States)
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Despite fundamental importance, the experimental characterization of the hydrogen bond network, particularly in multicomponent protic solutions, remains a challenge. Although recent work has experimentally validated that the oxygen K-edge X-ray absorption spectra is sensitive to local hydrogen bond patterns in pure water and aqueous alcohol solutions, the generality of this observation is unknown—as is the sensitivity to the electronic structure of the alcohol cosolvent. In this work, we investigate the electronic structure of water solvated alcohol model geometries using energy specific time-dependent density functional theory to calculate oxygen K-edge X-ray excitations. We find that the geometry of dangling hydrogen bonds in pure water is the main contributor to the pre-edge feature seen in the X-ray absorption spectra, agreeing with previous experimental and theoretical work. We then extend this result to solvated alcohol systems and observe a similar phenomenon, yet importantly, the increase of electron donation from alkyl chains to the alcohol OH group directly correlates to the strength of the core excitation on the dangling hydrogen bond model geometry. Finally, this trend arises from a stronger transition dipole moment due to electron localization on the OH group.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1566411
Alternate ID(s):
OSTI ID: 1770151; OSTI ID: 1596371; OSTI ID: 1472181
Journal Information:
International Journal of Quantum Chemistry, Journal Name: International Journal of Quantum Chemistry Journal Issue: 1 Vol. 119; ISSN 0020-7608
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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