Broadband 2D IR spectroscopy reveals dominant asymmetric H5O2+ proton hydration structures in acid solutions

Fournier, Joseph A.; Carpenter, William B.; Lewis, Nicholas H.  C.; Tokmakoff, Andrei

doi:10.1038/s41557-018-0091-y

Title: Broadband 2D IR spectroscopy reveals dominant asymmetric H₅O₂⁺ proton hydration structures in acid solutions

Abstract

Given its critical role in redox chemistry, determining the structure of the aqueous excess proton and the mechanism of proton transport in water remains an intense area of experimental and theoretical research. The ultrafast dynamics of the proton’s hydration structure has made experimental study extremely challenging. Using ultrafast broadband two-dimensional infrared spectroscopy, we show that the vibrational spectrum of the aqueous proton is fully consistent with a protonated water complex broadly defined as a Zundel like H₅O₂⁺ motif. Analysis of the inhomogeneously broadened proton stretch two-dimensional lineshape indicates an intrinsically asymmetric, low barrier O-H⁺-O potential that exhibits surprisingly persistent distributions in both its asymmetry and O-O distance. Finally, this structural characterization has direct implications for the extent of delocalization of the proton’s excess charge and possible mechanisms for proton transport in water.

Authors:

^[1];

^[1]

Univ. of Chicago, IL (United States). James Franck Inst., and Inst. for Biophysical, and Dept. of Chemistry

Publication Date:: Mon Jul 30 00:00:00 EDT 2018

Research Org.:: Univ. of Chicago, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:: 1480907

Grant/Contract Number:: SC0014305

Resource Type:: Accepted Manuscript

Journal Name:: Nature Chemistry

Additional Journal Information:: Journal Volume: 10; Journal Issue: 9; Journal ID: ISSN 1755-4330

Publisher:: Nature Publishing Group

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Fournier, Joseph A., Carpenter, William B., Lewis, Nicholas H.  C., and Tokmakoff, Andrei. Broadband 2D IR spectroscopy reveals dominant asymmetric H5O2+ proton hydration structures in acid solutions.  United States: N. p., 2018. 
Web.  doi:10.1038/s41557-018-0091-y.

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                    Fournier, Joseph A., Carpenter, William B., Lewis, Nicholas H.  C., & Tokmakoff, Andrei. Broadband 2D IR spectroscopy reveals dominant asymmetric H5O2+ proton hydration structures in acid solutions.  United States.  https://doi.org/10.1038/s41557-018-0091-y

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                    Fournier, Joseph A., Carpenter, William B., Lewis, Nicholas H.  C., and Tokmakoff, Andrei. Mon .  
"Broadband 2D IR spectroscopy reveals dominant asymmetric H5O2+ proton hydration structures in acid solutions".  United States.  https://doi.org/10.1038/s41557-018-0091-y.  https://www.osti.gov/servlets/purl/1480907.

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@article{osti_1480907,

  title        = {Broadband 2D IR spectroscopy reveals dominant asymmetric H5O2+ proton hydration structures in acid solutions},

  author       = {Fournier, Joseph A. and Carpenter, William B. and Lewis, Nicholas H.  C. and Tokmakoff, Andrei},

  abstractNote = {Given its critical role in redox chemistry, determining the structure of the aqueous excess proton and the mechanism of proton transport in water remains an intense area of experimental and theoretical research. The ultrafast dynamics of the proton’s hydration structure has made experimental study extremely challenging. Using ultrafast broadband two-dimensional infrared spectroscopy, we show that the vibrational spectrum of the aqueous proton is fully consistent with a protonated water complex broadly defined as a Zundel like H5O2+ motif. Analysis of the inhomogeneously broadened proton stretch two-dimensional lineshape indicates an intrinsically asymmetric, low barrier O-H+-O potential that exhibits surprisingly persistent distributions in both its asymmetry and O-O distance. Finally, this structural characterization has direct implications for the extent of delocalization of the proton’s excess charge and possible mechanisms for proton transport in water.},

  doi          = {10.1038/s41557-018-0091-y},

  journal      = {Nature Chemistry},

  number       = 9,

  volume       = 10,

  place        = {United States},

  year         = {Mon Jul 30 00:00:00 EDT 2018},

  month        = {Mon Jul 30 00:00:00 EDT 2018}

}

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Title: Broadband 2D IR spectroscopy reveals dominant asymmetric H5O2+ proton hydration structures in acid solutions

Abstract

Citation Formats

The vibrational spectrum of the hydrated proton: Comparison of experiment, simulation, and normal mode analysis journal, January 2002

Gas-Phase Infrared Spectrum of the Protonated Water Dimer journal, February 2003

Concerted Hydrogen-Bond Dynamics in the Transport Mechanism of the Hydrated Proton: A First-Principles Molecular Dynamics Study journal, November 2009

The Hydrated Excess Proton in the Zundel Cation H 5 O 2 + : The Role of Ultrafast Solvent Fluctuations journal, July 2016

Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations journal, September 2006

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Calculated frequencies and intensities associated with coupling of the proton motion with the hydrogen bond stretching vibration in a double minimum potential surface journal, January 1973

IR spectral assignments for the hydrated excess proton in liquid water journal, April 2017

Protons and Hydroxide Ions in Aqueous Systems journal, April 2016

Role of Charge Transfer in the Structure and Dynamics of the Hydrated Proton journal, April 2009

Ultrafast 2D IR spectroscopy of the excess proton in liquid water journal, October 2015

Unraveling Anharmonic Effects in the Vibrational Predissociation Spectra of H 5 O 2 + and Its Deuterated Analogues journal, June 2011

The nature of the hydrated excess proton in water journal, February 1999

The unique nature of H + in water journal, January 2011

Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water dimer. II. Infrared spectrum and vibrational dynamics journal, November 2007

The Grotthuss mechanism journal, October 1995

Et tu, Grotthuss! and other unfinished stories journal, August 2006

Large-amplitude transfer motion of hydrated excess protons mapped by ultrafast 2D IR spectroscopy journal, July 2017

Communication: VSCF/VCI vibrational spectroscopy of H 7 O 3 + and H 9 O 4 + using high-level, many-body potential energy surface and dipole moment surfaces journal, March 2017

Delocalization and stretch-bend mixing of the HOH bend in liquid water journal, August 2017

Decomposition of the Experimental Raman and Infrared Spectra of Acidic Water into Proton, Special Pair, and Counterion Contributions journal, October 2017

Isomer-Selective Detection of Hydrogen-Bond Vibrations in the Protonated Water Hexamer journal, May 2013

Extremely high polarizability of hydrogen bonds journal, April 1972

Spectroscopic snapshots of the proton-transfer mechanism in water journal, December 2016

The Role of Quantum Effects on Structural and Electronic Fluctuations in Neat and Charged Water journal, November 2014

Spectral Signatures of Hydrated Proton Vibrations in Water Clusters journal, June 2005

Infrared Spectrum of the Hydrated Proton in Water journal, December 2010

Energiebänder der tunnelnden Überschuß-Protonen in flüssigen Säuren. Eine IR-spektroskopische Untersuchung der Natur der Gruppierungen H 5 O 2 + journal, April 1968

Self-dissociation and protonic charge transport in water and journal, October 1958

Picosecond Proton Transfer Kinetics in Water Revealed with Ultrafast IR Spectroscopy journal, February 2018

Snapshots of Proton Accommodation at a Microscopic Water Surface: Understanding the Vibrational Spectral Signatures of the Charge Defect in Cryogenically Cooled H + (H 2 O) n =2–28 Clusters journal, July 2015

The Curious Case of the Hydrated Proton journal, August 2011

Molecular modeling and assignment of IR spectra of the hydrated excess proton in isotopically dilute water journal, October 2016

A ‘clusters-in-liquid’ method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions journal, November 2012

The Hydrated Excess Proton in the Zundel Cation H 5 O 2 + : The Role of Ultrafast Solvent Fluctuations journal, July 2016

Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations journal, February 2007

Full dimensional (15D) quantum-dynamical simulation of the protonated water-dimer II: infrared spectrum and vibrational dynamics text, January 2007

Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H-Bonding Liquid Observed by Transient 2D-IR Spectroscopy journal, November 2018

Identifying Eigen-like hydrated protons at negatively charged interfaces journal, January 2020

Unprecedented O:⇔:O compression and H↔H fragilization in Lewis solutions journal, January 2019

The solvation effect on the rattling behaviour of the hydrated excess proton in water journal, January 2019

Entropic barriers in the kinetics of aqueous proton transfer journal, July 2019

Aqueous charge injection: solvation bonding dynamics, molecular nonbond interactions, and extraordinary solute capabilities journal, October 2018

Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H‐Bonding Liquid Observed by Transient 2D‐IR Spectroscopy journal, November 2018

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Title: Broadband 2D IR spectroscopy reveals dominant asymmetric H₅O₂⁺ proton hydration structures in acid solutions

The vibrational spectrum of the hydrated proton: Comparison of experiment, simulation, and normal mode analysis
journal, January 2002

Gas-Phase Infrared Spectrum of the Protonated Water Dimer
journal, February 2003

Concerted Hydrogen-Bond Dynamics in the Transport Mechanism of the Hydrated Proton: A First-Principles Molecular Dynamics Study
journal, November 2009

The Hydrated Excess Proton in the Zundel Cation H ₅ O ₂ ⁺ : The Role of Ultrafast Solvent Fluctuations
journal, July 2016

Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations
journal, September 2006

Über den Zustand des Protons (Hydroniumions) in wäßriger Lösung*
journal, June 1954

Calculated frequencies and intensities associated with coupling of the proton motion with the hydrogen bond stretching vibration in a double minimum potential surface
journal, January 1973

IR spectral assignments for the hydrated excess proton in liquid water
journal, April 2017

Protons and Hydroxide Ions in Aqueous Systems
journal, April 2016

Role of Charge Transfer in the Structure and Dynamics of the Hydrated Proton
journal, April 2009

Ultrafast 2D IR spectroscopy of the excess proton in liquid water
journal, October 2015

Unraveling Anharmonic Effects in the Vibrational Predissociation Spectra of H ₅ O ₂ ⁺ and Its Deuterated Analogues
journal, June 2011

The nature of the hydrated excess proton in water
journal, February 1999

The unique nature of H ⁺ in water
journal, January 2011

Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water dimer. II. Infrared spectrum and vibrational dynamics
journal, November 2007

The Grotthuss mechanism
journal, October 1995

Et tu, Grotthuss! and other unfinished stories
journal, August 2006

Large-amplitude transfer motion of hydrated excess protons mapped by ultrafast 2D IR spectroscopy
journal, July 2017

Communication: VSCF/VCI vibrational spectroscopy of H ₇ O 3 + and H ₉ O 4 + using high-level, many-body potential energy surface and dipole moment surfaces
journal, March 2017

Delocalization and stretch-bend mixing of the HOH bend in liquid water
journal, August 2017

Decomposition of the Experimental Raman and Infrared Spectra of Acidic Water into Proton, Special Pair, and Counterion Contributions
journal, October 2017

Isomer-Selective Detection of Hydrogen-Bond Vibrations in the Protonated Water Hexamer
journal, May 2013

Extremely high polarizability of hydrogen bonds
journal, April 1972

Spectroscopic snapshots of the proton-transfer mechanism in water
journal, December 2016

The Role of Quantum Effects on Structural and Electronic Fluctuations in Neat and Charged Water
journal, November 2014

Spectral Signatures of Hydrated Proton Vibrations in Water Clusters
journal, June 2005

Infrared Spectrum of the Hydrated Proton in Water
journal, December 2010

Energiebänder der tunnelnden Überschuß-Protonen in flüssigen Säuren. Eine IR-spektroskopische Untersuchung der Natur der Gruppierungen H ₅ O ₂ ⁺
journal, April 1968

Self-dissociation and protonic charge transport in water and
journal, October 1958

Picosecond Proton Transfer Kinetics in Water Revealed with Ultrafast IR Spectroscopy
journal, February 2018

Snapshots of Proton Accommodation at a Microscopic Water Surface: Understanding the Vibrational Spectral Signatures of the Charge Defect in Cryogenically Cooled H ⁺ (H ₂ O) _{n =2–28} Clusters
journal, July 2015

The Curious Case of the Hydrated Proton
journal, August 2011

Molecular modeling and assignment of IR spectra of the hydrated excess proton in isotopically dilute water
journal, October 2016

A ‘clusters-in-liquid’ method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions
journal, November 2012

The Hydrated Excess Proton in the Zundel Cation H ₅ O ₂ ⁺ : The Role of Ultrafast Solvent Fluctuations
journal, July 2016

Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations
journal, February 2007

Full dimensional (15D) quantum-dynamical simulation of the protonated water-dimer II: infrared spectrum and vibrational dynamics
text, January 2007

Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H-Bonding Liquid Observed by Transient 2D-IR Spectroscopy
journal, November 2018

Identifying Eigen-like hydrated protons at negatively charged interfaces
journal, January 2020

Unprecedented O:⇔:O compression and H↔H fragilization in Lewis solutions
journal, January 2019

The solvation effect on the rattling behaviour of the hydrated excess proton in water
journal, January 2019

Entropic barriers in the kinetics of aqueous proton transfer
journal, July 2019

Aqueous charge injection: solvation bonding dynamics, molecular nonbond interactions, and extraordinary solute capabilities
journal, October 2018

Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H‐Bonding Liquid Observed by Transient 2D‐IR Spectroscopy
journal, November 2018

Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H-Bonding Liquid Observed by Transient 2D-IR Spectroscopy
text, January 2018

Tracking Aqueous Proton Transfer by Two-Dimensional Infrared Spectroscopy and ab Initio Molecular Dynamics Simulations
journal, May 2019

Hydrated Excess Proton Raman Spectral Densities Probed in Floating Water Bridges
journal, October 2018

Nature of Excess Hydrated Proton at the Water–Air Interface
journal, December 2019