DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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:1596371

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. 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); USDOE
Grant/Contract Number:
AC05-76RL01830; CHE-1565520; MRI-1624430
OSTI ID:
1596371
Alternate ID(s):
OSTI ID: 1472181; OSTI ID: 1566411
Journal Information:
International Journal of Quantum Chemistry, Vol. 119, Issue 1; ISSN 0020-7608
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

References (34)

The interpretation of X-ray absorption spectra of water and ice journal October 2002
Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules journal November 2005
A TRLFS Study on the Complexation of CmIII and EuIII with 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine in Water/Methanol Mixture journal May 2010
Electrospray mass spectrometry (ESI-MS) in the study of metal–ligand solution equilibria journal January 2006
Time Dependent Density Functional Theory of X-ray Absorption Spectroscopy of Alkaline-Earth Oxides journal May 2005
Hydrogen bond network topology in liquid water and methanol: a graph theory approach journal January 2013
The Structure of the First Coordination Shell in Liquid Water journal May 2004
Molecular segregation observed in a concentrated alcohol–water solution journal April 2002
Cluster formation and percolation in ethanol-water mixtures journal October 2017
Energy-Specific Equation-of-Motion Coupled-Cluster Methods for High-Energy Excited States: Application to K -edge X-ray Absorption Spectroscopy journal August 2015
Adsorption of fermentation inhibitors from lignocellulosic biomass hydrolyzates for improved ethanol yield and value-added product recovery journal June 2009
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Nearest-neighbor oxygen distances in liquid water and ice observed by x-ray Raman based extended x-ray absorption fine structure journal November 2007
Enhancement of retention by ion-pair formation in liquid chromatography with nonpolar stationary phases journal December 1977
On the collective properties of water molecules in one-dimensional zeolitic channels journal January 2001
Spectroscopic probing of local hydrogen-bonding structures in liquid water journal February 2002
Hydrogen bond networks in water and methanol with varying interaction strengths
  • da Silva, Juliana Angeiras Batista; Moreira, Francisco George Brady; dos Santos, Vivianni Marques Leite
  • Phys. Chem. Chem. Phys., Vol. 13, Issue 2 https://doi.org/10.1039/C0CP01204A
journal January 2011
An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules journal November 1998
Time-dependent density functional theory calculations of the spectroscopy of core electrons journal January 2010
Energy-Specific Linear Response TDHF/TDDFT for Calculating High-Energy Excited States journal October 2011
Lattice model for water-solute mixtures journal October 2016
A new mixing of Hartree–Fock and local density‐functional theories journal January 1993
Electrophoretic mobilities of cationic analytes in non-aqueous methanol, acetonitrile and their mixtures journal July 2001
Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy journal May 2016
Time-resolved X-ray absorption spectroscopy of infrared-laser-induced temperature jumps in liquid water journal May 2009
Time-Dependent Density Functional Response Theory for Molecules book November 1995
Water–methanol mixtures: topology of hydrogen bonded network journal January 2008
Calibration of Energy-Specific TDDFT for Modeling K-edge XAS Spectra of Light Elements journal June 2015
Water–Methanol Mixtures: Simulations of Mixing Properties over the Entire Range of Mole Fractions journal June 2015
Deconstructing Hydrogen-Bond Networks in Confined Nanoporous Materials: Implications for Alcohol–Water Separation journal August 2014
X-ray Absorption Spectroscopy of Titanium Oxide by Time Dependent Density Functional Calculations journal May 2006
Bonded-atom fragments for describing molecular charge densities journal January 1977
Multicomponent Adsorption of Alcohols onto Silicalite-1 from Aqueous Solution: Isotherms, Structural Analysis, and Assessment of Ideal Adsorbed Solution Theory journal October 2012
Natural transition orbitals journal March 2003

Figures / Tables (2)