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

Abstract

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.

Authors:
 [1];  [2]; ORCiD logo [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
  2. Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington D.C. (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Battelle Memorial Institute, Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566411
Alternate Identifier(s):
OSTI ID: 1472181
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
International Journal of Quantum Chemistry
Additional Journal Information:
Journal Volume: 119; Journal Issue: 1; Journal ID: ISSN 0020-7608
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nuclear; separations; water; materials and chemistry by design; co-solvent; hydrogen bond; TDDFT; XAS

Citation Formats

Stetina, Torin F., Clark, Aurora E., and Li, Xiaosong. X-ray absorption signatures of hydrogen-bond structure in water-alcohol solutions. United States: N. p., 2018. Web. doi:10.1002/qua.25802.
Stetina, Torin F., Clark, Aurora E., & Li, Xiaosong. X-ray absorption signatures of hydrogen-bond structure in water-alcohol solutions. United States. doi:10.1002/qua.25802.
Stetina, Torin F., Clark, Aurora E., and Li, Xiaosong. Sat . "X-ray absorption signatures of hydrogen-bond structure in water-alcohol solutions". United States. doi:10.1002/qua.25802. https://www.osti.gov/servlets/purl/1566411.
@article{osti_1566411,
title = {X-ray absorption signatures of hydrogen-bond structure in water-alcohol solutions},
author = {Stetina, Torin F. and Clark, Aurora E. and Li, Xiaosong},
abstractNote = {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.},
doi = {10.1002/qua.25802},
journal = {International Journal of Quantum Chemistry},
number = 1,
volume = 119,
place = {United States},
year = {2018},
month = {9}
}

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