skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy

Abstract

We employed ultrafast transient absorption and broadband 2DIR spectroscopy to study the vibrational dynamics of aqueous hydroxide solutions by exciting the O–H stretch vibrations of the strongly hydrogen-bonded hydroxide solvation shell water and probing the continuum absorption of the solvated ion between 1500 and 3800 cm{sup −1}. We observe rapid vibrational relaxation processes on 150–250 fs time scales across the entire probed spectral region as well as slower vibrational dynamics on 1–2 ps time scales. Furthermore, the O–H stretch excitation loses its frequency memory in 180 fs, and vibrational energy exchange between bulk-like water vibrations and hydroxide-associated water vibrations occurs in ∼200 fs. The fast dynamics in this system originate in strong nonlinear coupling between intra- and intermolecular vibrations and are explained in terms of non-adiabatic vibrational relaxation. These measurements indicate that the vibrational dynamics of the aqueous hydroxide complex are faster than the time scales reported for long-range transport of protons in aqueous hydroxide solutions.

Authors:
 [1];  [1]
  1. Department of Chemistry, James Franck Institute, and Institute for Biophysical Dynamics, University of Chicago, Chicago, Illinois 60637 (United States)
Publication Date:
OSTI Identifier:
22493253
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 19; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ABSORPTION SPECTROSCOPY; CHEMICAL BONDS; COMPLEXES; COUPLING; ENERGY TRANSFER; EXCITATION; HYDROGEN; HYDROXIDES; INFRARED SPECTRA; LONG-RANGE TRANSPORT; NONLINEAR PROBLEMS; PROBES; PROTONS; RELAXATION; SOLUTIONS; SOLVATION; TRANSIENTS; WATER

Citation Formats

Mandal, Aritra, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, and Tokmakoff, Andrei. Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy. United States: N. p., 2015. Web. doi:10.1063/1.4935174.
Mandal, Aritra, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, & Tokmakoff, Andrei. Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy. United States. https://doi.org/10.1063/1.4935174
Mandal, Aritra, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, and Tokmakoff, Andrei. 2015. "Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy". United States. https://doi.org/10.1063/1.4935174.
@article{osti_22493253,
title = {Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy},
author = {Mandal, Aritra and Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 and Tokmakoff, Andrei},
abstractNote = {We employed ultrafast transient absorption and broadband 2DIR spectroscopy to study the vibrational dynamics of aqueous hydroxide solutions by exciting the O–H stretch vibrations of the strongly hydrogen-bonded hydroxide solvation shell water and probing the continuum absorption of the solvated ion between 1500 and 3800 cm{sup −1}. We observe rapid vibrational relaxation processes on 150–250 fs time scales across the entire probed spectral region as well as slower vibrational dynamics on 1–2 ps time scales. Furthermore, the O–H stretch excitation loses its frequency memory in 180 fs, and vibrational energy exchange between bulk-like water vibrations and hydroxide-associated water vibrations occurs in ∼200 fs. The fast dynamics in this system originate in strong nonlinear coupling between intra- and intermolecular vibrations and are explained in terms of non-adiabatic vibrational relaxation. These measurements indicate that the vibrational dynamics of the aqueous hydroxide complex are faster than the time scales reported for long-range transport of protons in aqueous hydroxide solutions.},
doi = {10.1063/1.4935174},
url = {https://www.osti.gov/biblio/22493253}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 19,
volume = 143,
place = {United States},
year = {Sat Nov 21 00:00:00 EST 2015},
month = {Sat Nov 21 00:00:00 EST 2015}
}

Works referencing / citing this record:

Acetate ion and its interesting solvation shell structure and dynamics
journal, March 2018