Ultrafast 2D IR spectroscopy of the excess proton in liquid water

Thamer, M.; De Marco, L.; Ramasesha, K.; Mandal, A.; Tokmakoff, A.

doi:10.1126/science.aab3908

Title: Ultrafast 2D IR spectroscopy of the excess proton in liquid water

Authors:: Thamer, M.; De Marco, L.; Ramasesha, K.; Mandal, A.; Tokmakoff, A.

Publication Date:: 2015-10-01

Sponsoring Org.:: USDOE

OSTI Identifier:: 1355823

Grant/Contract Number:: SC0011456; SC0014305

Resource Type:: Published Article

Journal Name:: Science

Additional Journal Information:: Journal Name: Science Journal Volume: 350 Journal Issue: 6256; Journal ID: ISSN 0036-8075

Publisher:: American Association for the Advancement of Science (AAAS)

Country of Publication:: United States

Language:: English

Citation Formats


                    Thamer, M., De Marco, L., Ramasesha, K., Mandal, A., and Tokmakoff, A. Ultrafast 2D IR spectroscopy of the excess proton in liquid water.  United States: N. p., 2015. 
        Web.  doi:10.1126/science.aab3908.

Copy to clipboard


                    Thamer, M., De Marco, L., Ramasesha, K., Mandal, A., & Tokmakoff, A. Ultrafast 2D IR spectroscopy of the excess proton in liquid water.  United States.  doi:https://doi.org/10.1126/science.aab3908

Copy to clipboard


                    Thamer, M., De Marco, L., Ramasesha, K., Mandal, A., and Tokmakoff, A. Thu .  
        "Ultrafast 2D IR spectroscopy of the excess proton in liquid water".  United States.  doi:https://doi.org/10.1126/science.aab3908.

Copy to clipboard


                    
@article{osti_1355823,

  title        = {Ultrafast 2D IR spectroscopy of the excess proton in liquid water},

  author       = {Thamer, M. and De Marco, L. and Ramasesha, K. and Mandal, A. and Tokmakoff, A.},

  abstractNote = {},

  doi          = {10.1126/science.aab3908},

  journal      = {Science},

  number       = 6256,

  volume       = 350,

  place        = {United States},

  year         = {2015},

  month        = {10}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
DOI: https://doi.org/10.1126/science.aab3908

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 89 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

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

Kim, Jeongho; Schmitt, Udo W.; Gruetzmacher, Julie A.
The Journal of Chemical Physics, Vol. 116, Issue 2
DOI: 10.1063/1.1423327

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

Asmis, K. R.
Science, Vol. 299, Issue 5611
DOI: 10.1126/science.1081634

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

Berkelbach, Timothy C.; Lee, Hee-Seung; Tuckerman, Mark E.
Physical Review Letters, Vol. 103, Issue 23
DOI: 10.1103/PhysRevLett.103.238302

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

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

Marx, Dominik
ChemPhysChem, Vol. 7, Issue 9
DOI: 10.1002/cphc.200600128

Molecular Mechanism of HCl Acid Ionization in Water: Ab Initio Potential Energy Surfaces and Monte Carlo Simulations
journal, December 1997

Ando, Koji; Hynes, James T.
The Journal of Physical Chemistry B, Vol. 101, Issue 49
DOI: 10.1021/jp970173j

Ultrafast Vibrational and Structural Dynamics of the Proton in Liquid Water
journal, April 2006

Woutersen, Sander; Bakker, Huib J.
Physical Review Letters, Vol. 96, Issue 13
DOI: 10.1103/PhysRevLett.96.138305

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

Janoschek, R.; Weidemann, Erich G.; Zundel, Georg
Journal of the Chemical Society, Faraday Transactions 2, Vol. 69
DOI: 10.1039/f29736900505

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

Fecko, C. J.; Loparo, J. J.; Tokmakoff, A.
Optics Communications, Vol. 241, Issue 4-6
DOI: 10.1016/j.optcom.2004.07.038

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

Petersen, Poul B.; Tokmakoff, Andrei
Optics Letters, Vol. 35, Issue 12
DOI: 10.1364/OL.35.001962

Time-resolved observation of the Eigen cation in liquid water
journal, January 2007

Amir, Wafa; Gallot, Guilhem; Hache, François
The Journal of Chemical Physics, Vol. 126, Issue 3
DOI: 10.1063/1.2428299

Potential energy surfaces and vibrational spectra of H5O2+ and larger hydrated proton complexes
journal, February 1995

Ojam�e, Lars; Shavitt, Isaiah; Singer, Sherwin J.
International Journal of Quantum Chemistry, Vol. 56, Issue S29
DOI: 10.1002/qua.560560872

Frequency-frequency correlation functions and apodization in two-dimensional infrared vibrational echo spectroscopy: A new approach
journal, September 2007

Kwak, Kyungwon; Park, Sungnam; Finkelstein, Ilya J.
The Journal of Chemical Physics, Vol. 127, Issue 12
DOI: 10.1063/1.2772269

Ab Initio Molecular Dynamics Simulation of the Solvation and Transport of H3O+ and OH- Ions in Water
journal, April 1995

Tuckerman, Mark; Laasonen, Kari; Sprik, Michiel
The Journal of Physical Chemistry, Vol. 99, Issue 16
DOI: 10.1021/j100016a003

The Structure of the Hydrogen Ion (H _aq ⁺ ) in Water
journal, February 2010

Stoyanov, Evgenii S.; Stoyanova, Irina V.; Reed, Christopher A.
Journal of the American Chemical Society, Vol. 132, Issue 5
DOI: 10.1021/ja9101826

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

Guasco, Timothy L.; Johnson, Mark A.; McCoy, Anne B.
The Journal of Physical Chemistry A, Vol. 115, Issue 23
DOI: 10.1021/jp109999b

Eigen and Zundel Forms of Small Protonated Water Clusters: Structures and Infrared Spectra
journal, October 2007

Park, Mina; Shin, Ilgyou; Singh, N. Jiten
The Journal of Physical Chemistry A, Vol. 111, Issue 42
DOI: 10.1021/jp073912x

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

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

Marx, Dominik; Tuckerman, Mark E.; Hutter, Jürg
Nature, Vol. 397, Issue 6720
DOI: 10.1038/17579

An extended empirical valence bond model for describing proton transfer in H+(H2O)n clusters and liquid water
journal, February 1998

Vuilleumier, Rodolphe; Borgis, Daniel
Chemical Physics Letters, Vol. 284, Issue 1-2
DOI: 10.1016/S0009-2614(97)01365-1

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

Vendrell, Oriol; Gatti, Fabien; Meyer, Hans-Dieter
The Journal of Chemical Physics, Vol. 127, Issue 18
DOI: 10.1063/1.2787596

The Grotthuss mechanism
journal, October 1995

Agmon, Noam
Chemical Physics Letters, Vol. 244, Issue 5-6
DOI: 10.1016/0009-2614(95)00905-J

Unusual “Amphiphilic” Association of Hydrated Protons in Strong Acid Solution
journal, March 2008

Wang, Feng; Izvekov, Sergei; Voth, Gregory A.
Journal of the American Chemical Society, Vol. 130, Issue 10
DOI: 10.1021/ja078106i

Kinetics of Proton Transport in Water
journal, April 2003

Kornyshev, A. A.; Kuznetsov, A. M.; Spohr, E.
The Journal of Physical Chemistry B, Vol. 107, Issue 15
DOI: 10.1021/jp020857d

A bond-order analysis of the mechanism for hydrated proton mobility in liquid water
journal, January 2005

Lapid, Hadas; Agmon, Noam; Petersen, Matt K.
The Journal of Chemical Physics, Vol. 122, Issue 1
DOI: 10.1063/1.1814973

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

Headrick, J. M.
Science, Vol. 308, Issue 5729
DOI: 10.1126/science.1113094

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

Xu, Jianqing; Zhang, Yong; Voth, Gregory A.
The Journal of Physical Chemistry Letters, Vol. 2, Issue 2
DOI: 10.1021/jz101536b

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

Persistent Ion Pairing in Aqueous Hydrochloric Acid
journal, June 2014

Baer, Marcel D.; Fulton, John L.; Balasubramanian, Mahalingam
The Journal of Physical Chemistry B, Vol. 118, Issue 26
DOI: 10.1021/jp501091h

Special Pair Dance and Partner Selection: Elementary Steps in Proton Transport in Liquid Water
journal, August 2008

Markovitch, Omer; Chen, Hanning; Izvekov, Sergei
The Journal of Physical Chemistry B, Vol. 112, Issue 31
DOI: 10.1021/jp804018y

Autoionization in Liquid Water
journal, March 2001

Geissler, P. L.
Science, Vol. 291, Issue 5511
DOI: 10.1126/science.1056991

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

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

Kulig, Waldemar; Agmon, Noam
Nature Chemistry, Vol. 5, Issue 1
DOI: 10.1038/nchem.1503

Similar Records in DOE PAGES and OSTI.GOV collections:

Picosecond Proton Transfer Kinetics in Water Revealed with Ultrafast IR Spectroscopy

Journal Article Carpenter, William B. ; Fournier, Joseph A. ; Lewis, Nicholas H. C. ; ... - Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Aqueous proton transport involves the ultrafast interconversion of hydrated proton species that are closely linked to the hydrogen bond dynamics of water, which has been a long-standing challenge to experiments. In this study, we use ultrafast IR spectroscopy to investigate the distinct vibrational transition centered at 1750 cm^–1 in strong acid solutions, which arises from bending vibrations of the hydrated proton complex. Broadband ultrafast two-dimensional IR spectroscopy and transient absorption are used to measure vibrational relaxation, spectral diffusion, and orientational relaxation dynamics. The hydrated proton bend displays fast vibrational relaxation and spectral diffusion timescales of 200–300 fs; however, the transientmore »« less
Cited by 19
DOI: https://doi.org/10.1021/acs.jpcb.8b00118

Full Text Available
IR spectral assignments for the hydrated excess proton in liquid water

Journal Article Biswas, Rajib ; Carpenter, William ; Fournier, Joseph A. ; ... - Journal of Chemical Physics

The local environmental sensitivity of infrared (IR) spectroscopy to a hydrogen-bonding structure makes it a powerful tool for investigating the structure and dynamics of excess protons in water. Although of significant interest, the line broadening that results from the ultrafast evolution of different solvated proton-water structures makes the assignment of liquid-phase IR spectra a challenging task. In this work, we apply a normal mode analysis using density functional theory of thousands of proton-water clusters taken from reactive molecular dynamics trajectories of the latest generation multistate empirical valence bond proton model (MS-EVB 3.2). These calculations are used to obtain a vibrationalmore »« less
Cited by 8
DOI: https://doi.org/10.1063/1.4980121

Full Text Available
Interplay of Ion–Water and Water–Water Interactions within the Hydration Shells of Nitrate and Carbonate Directly Probed with 2D IR Spectroscopy

Journal Article Fournier, Joseph A. ; Carpenter, William ; De Marco, Luigi ; ... - Journal of the American Chemical Society

The long-range influence of ions in solution on the water hydrogen-bond (H-bond) network remains a topic of vigorous debate. Recent spectroscopic and theoretical studies have, for the most part, reached the consensus that weakly coordinating ions only affect water molecules in the first hydration shell. In this work, we apply ultrafast broadband two-dimensional infrared (2D IR) spectroscopy to aqueous nitrate and carbonate in neat H₂O to study the solvation structure and dynamics of ions on opposite ends of the Hofmeister series. By exciting both the water OH stretches and ion stretches and probing the associated cross-peaks between them, we aremore »« less
Cited by 38
DOI: https://doi.org/10.1021/jacs.6b05122

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

Journal Article Fournier, Joseph A. ; Carpenter, William B. ; Lewis, Nicholas H. C. ; ... - Nature Chemistry

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 distributionsmore »« less
Cited by 17
DOI: https://doi.org/10.1038/s41557-018-0091-y

Full Text Available
Molecular modeling and assignment of IR spectra of the hydrated excess proton in isotopically dilute water

Journal Article Biswas, Rajib ; Carpenter, William ; Voth, Gregory A. ; ... - Journal of Chemical Physics

Infrared (IR) spectroscopy of the water O–H stretch has been widely used to probe both the local hydrogen-bonding structure and dynamics of aqueous systems. Although of significant interest, the IR spectroscopy of excess protons in water remains difficult to assign as a result of extensive and strong intermolecular interactions in hydrated proton complexes. As an alternate approach, we develop a mixed quantum-classical model for the vibrational spectroscopy of the excess proton in isotopically dilute water that draws on frozen proton-water clusters taken from reactive molecular dynamics trajectories of the latest generation multi-state empirical valence bond proton model (MS-EVB 3.2). Amore »« less
DOI: https://doi.org/10.1063/1.4964723

Full Text Available

Similar Records

Title: Ultrafast 2D IR spectroscopy of the excess proton in liquid water

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

Proton transfer through the water gossamer journal, July 2013

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

Molecular Mechanism of HCl Acid Ionization in Water: Ab Initio Potential Energy Surfaces and Monte Carlo Simulations journal, December 1997

Ultrafast Vibrational and Structural Dynamics of the Proton in Liquid Water journal, April 2006

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

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

Time-resolved observation of the Eigen cation in liquid water journal, January 2007

Potential energy surfaces and vibrational spectra of H5O2+ and larger hydrated proton complexes journal, February 1995

Frequency-frequency correlation functions and apodization in two-dimensional infrared vibrational echo spectroscopy: A new approach journal, September 2007

Ab Initio Molecular Dynamics Simulation of the Solvation and Transport of H3O+ and OH- Ions in Water journal, April 1995

The Structure of the Hydrogen Ion (H aq + ) in Water journal, February 2010

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

Eigen and Zundel Forms of Small Protonated Water Clusters: Structures and Infrared Spectra journal, October 2007

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

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

An extended empirical valence bond model for describing proton transfer in H+(H2O)n clusters and liquid water journal, February 1998

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

Unusual “Amphiphilic” Association of Hydrated Protons in Strong Acid Solution journal, March 2008

Kinetics of Proton Transport in Water journal, April 2003

A bond-order analysis of the mechanism for hydrated proton mobility in liquid water journal, January 2005

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

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

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

Persistent Ion Pairing in Aqueous Hydrochloric Acid journal, June 2014

Special Pair Dance and Partner Selection: Elementary Steps in Proton Transport in Liquid Water journal, August 2008

Autoionization in Liquid Water journal, March 2001

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

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

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

Proton transfer through the water gossamer
journal, July 2013

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

Molecular Mechanism of HCl Acid Ionization in Water: Ab Initio Potential Energy Surfaces and Monte Carlo Simulations
journal, December 1997

Ultrafast Vibrational and Structural Dynamics of the Proton in Liquid Water
journal, April 2006

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

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

Time-resolved observation of the Eigen cation in liquid water
journal, January 2007

Potential energy surfaces and vibrational spectra of H5O2+ and larger hydrated proton complexes
journal, February 1995

Frequency-frequency correlation functions and apodization in two-dimensional infrared vibrational echo spectroscopy: A new approach
journal, September 2007

Ab Initio Molecular Dynamics Simulation of the Solvation and Transport of H3O+ and OH- Ions in Water
journal, April 1995

The Structure of the Hydrogen Ion (H _aq ⁺ ) in Water
journal, February 2010

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

Eigen and Zundel Forms of Small Protonated Water Clusters: Structures and Infrared Spectra
journal, October 2007

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

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

An extended empirical valence bond model for describing proton transfer in H+(H2O)n clusters and liquid water
journal, February 1998

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

Unusual “Amphiphilic” Association of Hydrated Protons in Strong Acid Solution
journal, March 2008

Kinetics of Proton Transport in Water
journal, April 2003

A bond-order analysis of the mechanism for hydrated proton mobility in liquid water
journal, January 2005

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

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

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

Persistent Ion Pairing in Aqueous Hydrochloric Acid
journal, June 2014

Special Pair Dance and Partner Selection: Elementary Steps in Proton Transport in Liquid Water
journal, August 2008

Autoionization in Liquid Water
journal, March 2001

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

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