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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-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];  [2]
  1. Univ. of Chicago, IL (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1469646
Alternate Identifier(s):
OSTI ID: 1226104
Grant/Contract Number:  
SC0011456; SC0014305
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mandal, Aritra, and Tokmakoff, Andrei. Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy. United States: N. p., 2015. Web. https://doi.org/10.1063/1.4935174.
Mandal, Aritra, & Tokmakoff, Andrei. Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy. United States. https://doi.org/10.1063/1.4935174
Mandal, Aritra, and Tokmakoff, Andrei. Mon . "Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy". United States. https://doi.org/10.1063/1.4935174. https://www.osti.gov/servlets/purl/1469646.
@article{osti_1469646,
title = {Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy},
author = {Mandal, Aritra 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-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},
journal = {Journal of Chemical Physics},
number = 19,
volume = 143,
place = {United States},
year = {2015},
month = {11}
}

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Cited by: 8 works
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Works referenced in this record:

Observation of a Zundel-like transition state during proton transfer in aqueous hydroxide solutions
journal, July 2009

  • Roberts, S. T.; Petersen, P. B.; Ramasesha, K.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 36
  • DOI: 10.1073/pnas.0901571106

Molecular picture of hydroxide anion hydration in aqueous solutions studied by FT-IR ATR spectroscopy
journal, May 2007


Proton Defect Solvation and Dynamics in Aqueous Acid and Base
journal, October 2012

  • Kale, Seyit; Herzfeld, Judith
  • Angewandte Chemie International Edition, Vol. 51, Issue 44
  • DOI: 10.1002/anie.201203568

From The Cover: Hydration and mobility of HO-(aq)
journal, April 2004

  • Asthagiri, D.; Pratt, L. R.; Kress, J. D.
  • Proceedings of the National Academy of Sciences, Vol. 101, Issue 19
  • DOI: 10.1073/pnas.0401696101

Origin of the 900 cm −1 broad double-hump OH vibrational feature of strongly hydrogen-bonded carboxylic acids
journal, March 2015

  • Van Hoozen, Brian L.; Petersen, Poul B.
  • The Journal of Chemical Physics, Vol. 142, Issue 10
  • DOI: 10.1063/1.4914147

Generation of 45 femtosecond pulses at 3 μm with a KNbO3 optical parametric amplifier
journal, November 2004


Source for ultrafast continuum infrared and terahertz radiation
journal, January 2010


A multistate empirical valence bond model for solvation and transport simulations of OH− in aqueous solutions
journal, January 2009

  • Ufimtsev, Ivan S.; Kalinichev, Andrey G.; Martinez, Todd J.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 41
  • DOI: 10.1039/b907859b

The hydration state of HO−(aq)
journal, October 2003


A charged ring model for classical OH−(aq) simulations
journal, July 2007

  • Ufimtsev, Ivan S.; Kalinichev, Andrey G.; Martinez, Todd J.
  • Chemical Physics Letters, Vol. 442, Issue 1-3
  • DOI: 10.1016/j.cplett.2007.05.042

Water as an Active Constituent in Cell Biology
journal, January 2008


Water vibrations have strongly mixed intra- and intermolecular character
journal, September 2013

  • Ramasesha, Krupa; De Marco, Luigi; Mandal, Aritra
  • Nature Chemistry, Vol. 5, Issue 11
  • DOI: 10.1038/nchem.1757

Local dynamics and structure of the solvated hydroxide ion in water
journal, January 2010


Hydroxide Ion Hydration in Aqueous Solutions
journal, April 2007

  • Śmiechowski, Maciej; Stangret, Janusz
  • The Journal of Physical Chemistry A, Vol. 111, Issue 15
  • DOI: 10.1021/jp0659397

Very polarisable hydrogen bonds in solutions of bases having infra-red absorption continua
journal, January 1973

  • Schiöberg, Dag; Zundel, Georg
  • J. Chem. Soc., Faraday Trans. 2, Vol. 69, Issue 0
  • DOI: 10.1039/f29736900771

Designing Advanced Alkaline Polymer Electrolytes for Fuel Cell Applications
journal, October 2011

  • Pan, Jing; Chen, Chen; Zhuang, Lin
  • Accounts of Chemical Research, Vol. 45, Issue 3
  • DOI: 10.1021/ar200201x

Local and Collective Reaction Coordinates in the Transport of the Aqueous Hydroxide Ion
journal, April 2014

  • Roberts, Sean T.; Mandal, Aritra; Tokmakoff, Andrei
  • The Journal of Physical Chemistry B, Vol. 118, Issue 28
  • DOI: 10.1021/jp501145p

Two-dimensional infrared spectroscopy of isotope-diluted ice Ih
journal, May 2011

  • Perakis, Fivos; Widmer, Susanne; Hamm, Peter
  • The Journal of Chemical Physics, Vol. 134, Issue 20
  • DOI: 10.1063/1.3592561

Potential Function Model of Hydrogen Bonds. II
journal, July 1957

  • Schroeder, Rudolph; Lippincott, Ellis R.
  • The Journal of Physical Chemistry, Vol. 61, Issue 7
  • DOI: 10.1021/j150553a017

Connecting Solvation Shell Structure to Proton Transport Kinetics in Hydrogen–Bonded Networks via Population Correlation Functions
journal, October 2007


Ultrafast Vibrational Dynamics of Hydrogen Bonds in the Condensed Phase
journal, April 2004

  • Nibbering, Erik T. J.; Elsaesser, Thomas
  • Chemical Reviews, Vol. 104, Issue 4
  • DOI: 10.1021/cr020694p

Ultrafast coherent nuclear motions of hydrogen bonded carboxylic acid dimers
journal, February 2003


The nature and transport mechanism of hydrated hydroxide ions in aqueous solution
journal, June 2002

  • Tuckerman, Mark E.; Marx, Dominik; Parrinello, Michele
  • Nature, Vol. 417, Issue 6892
  • DOI: 10.1038/nature00797

H+ and OH− ions in aqueous solutions vibrational spectra of hydrates
journal, June 1979


Ultrafast Energy Equilibration in Hydrogen-Bonded Liquids
journal, March 2001

  • Lock, A. J.; Woutersen, S.; Bakker, H. J.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 8
  • DOI: 10.1021/jp003158e

Transport Properties of Hydroxide and Proton Conducting Membranes
journal, April 2008

  • Hibbs, Michael R.; Hickner, Michael A.; Alam, Todd M.
  • Chemistry of Materials, Vol. 20, Issue 7
  • DOI: 10.1021/cm703263n

First-Principles Study of Aqueous Hydroxide Solutions
journal, July 2002

  • Chen, Bin; Park, Jung Mee; Ivanov, Ivaylo
  • Journal of the American Chemical Society, Vol. 124, Issue 29
  • DOI: 10.1021/ja020350g

Vibrational conical intersections in the water dimer
journal, April 2013


Proton transfer through the water gossamer
journal, July 2013

  • Hassanali, Ali; Giberti, Federico; Cuny, Jérôme
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 34
  • DOI: 10.1073/pnas.1306642110

Aqueous Basic Solutions: Hydroxide Solvation, Structural Diffusion, and Comparison to the Hydrated Proton
journal, April 2010

  • Marx, Dominik; Chandra, Amalendu; Tuckerman, Mark E.
  • Chemical Reviews, Vol. 110, Issue 4
  • DOI: 10.1021/cr900233f

Proton Solvation and Transport in Aqueous and Biomolecular Systems:  Insights from Computer Simulations
journal, May 2007

  • Swanson, Jessica M. J.; Maupin, C. Mark; Chen, Hanning
  • The Journal of Physical Chemistry B, Vol. 111, Issue 17
  • DOI: 10.1021/jp070104x

Ab initio molecular dynamics simulation of the solvation and transport of hydronium and hydroxyl ions in water
journal, July 1995

  • Tuckerman, M.; Laasonen, K.; Sprik, M.
  • The Journal of Chemical Physics, Vol. 103, Issue 1
  • DOI: 10.1063/1.469654

Ultrafast 2D-IR vibrational echo spectroscopy: a probe of molecular dynamics
journal, October 2007


Solvation Structure and Mobility Mechanism of OH - :  A Car−Parrinello Molecular Dynamics Investigation of Alkaline Solutions
journal, November 2002

  • Chen, Bin; Ivanov, Ivaylo; Park, Jung Mee
  • The Journal of Physical Chemistry B, Vol. 106, Issue 46
  • DOI: 10.1021/jp026504w

One‐Dimensional Model of the Hydrogen Bond
journal, June 1955

  • Lippincott, Ellis R.; Schroeder, Rudolph
  • The Journal of Chemical Physics, Vol. 23, Issue 6
  • DOI: 10.1063/1.1742196

Proton Transfer in Concentrated Aqueous Hydroxide Visualized Using Ultrafast Infrared Spectroscopy
journal, April 2011

  • Roberts, Sean T.; Ramasesha, Krupa; Petersen, Poul B.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 16
  • DOI: 10.1021/jp108474p

Multidimensional infrared spectroscopy of water. II. Hydrogen bond switching dynamics
journal, November 2006

  • Loparo, Joseph J.; Roberts, Sean T.; Tokmakoff, Andrei
  • The Journal of Chemical Physics, Vol. 125, Issue 19
  • DOI: 10.1063/1.2382896

Collective vibrations of water-solvated hydroxide ions investigated with broadband 2DIR spectroscopy
journal, May 2014

  • Mandal, Aritra; Ramasesha, Krupa; De Marco, Luigi
  • The Journal of Chemical Physics, Vol. 140, Issue 20
  • DOI: 10.1063/1.4878490

Energy Relaxation Dynamics of the Hydration Complex of Hydroxide
journal, December 2011

  • Liu, Liyuan; Hunger, Johannes; Bakker, Huib J.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 51
  • DOI: 10.1021/jp2070248

Vibrational Multilevel Quantum Coherence due to Anharmonic Couplings in Intermolecular Hydrogen Bonds
journal, November 2003


Dynamics of water molecules in an alkaline environment
journal, November 2002

  • Nienhuys, Han-Kwang; Lock, Arjan J.; van Santen, Rutger A.
  • The Journal of Chemical Physics, Vol. 117, Issue 17
  • DOI: 10.1063/1.1510670

Structure and Dynamics of OH - (aq)
journal, February 2006

  • Tuckerman, Mark E.; Chandra, Amalendu; Marx, Dominik
  • Accounts of Chemical Research, Vol. 39, Issue 2
  • DOI: 10.1021/ar040207n

Two-dimensional Fourier transform spectroscopy in the pump-probe geometry
journal, January 2007

  • DeFlores, Lauren P.; Nicodemus, Rebecca A.; Tokmakoff, Andrei
  • Optics Letters, Vol. 32, Issue 20
  • DOI: 10.1364/OL.32.002966

Three-dimensional infrared spectroscopy of isotope-diluted ice Ih
journal, July 2013

  • Perakis, Fivos; Borek, Joanna A.; Hamm, Peter
  • The Journal of Chemical Physics, Vol. 139, Issue 1
  • DOI: 10.1063/1.4812216

Autoionization in Liquid Water
journal, March 2001


Mechanism of hydroxide mobility
journal, March 2000


    Works referencing / citing this record:

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

    • Zhang, Xiaoliu; Kumar, Revati; Kuroda, Daniel G.
    • The Journal of Chemical Physics, Vol. 148, Issue 9
    • DOI: 10.1063/1.5019363