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

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

Journal Article · Mon Jul 30 00:00:00 EDT 2018 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-018-0091-y· OSTI ID:1480907

^[1]; ^[2]; ^[2]; ^[2]

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

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0014305

OSTI ID:: 1480907

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 9 Vol. 10; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (38)

The Hydrated Excess Proton in the Zundel Cation H ₅ O ₂ ⁺ : The Role of Ultrafast Solvent Fluctuations Dahms, Fabian; Costard, Rene; Pines, Ehud Angewandte Chemie, Vol. 128, Issue 36 https://doi.org/10.1002/ange.201602523	journal	July 2016
The Hydrated Excess Proton in the Zundel Cation H ₅ O ₂ ⁺ : The Role of Ultrafast Solvent Fluctuations Dahms, Fabian; Costard, Rene; Pines, Ehud Angewandte Chemie International Edition, Vol. 55, Issue 36 https://doi.org/10.1002/anie.201602523	journal	July 2016
Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations Marx, Dominik ChemPhysChem, Vol. 7, Issue 9 https://doi.org/10.1002/cphc.200600128	journal	September 2006
Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations Marx, Dominik ChemPhysChem, Vol. 8, Issue 2 https://doi.org/10.1002/cphc.200790002	journal	February 2007
The Grotthuss mechanism Agmon, Noam Chemical Physics Letters, Vol. 244, Issue 5-6 https://doi.org/10.1016/0009-2614(95)00905-J	journal	October 1995
Et tu, Grotthuss! and other unfinished stories Cukierman, Samuel Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1757, Issue 8 https://doi.org/10.1016/j.bbabio.2005.12.001	journal	August 2006
Protons and Hydroxide Ions in Aqueous Systems Agmon, Noam; Bakker, Huib J.; Campen, R. Kramer Chemical Reviews, Vol. 116, Issue 13 https://doi.org/10.1021/acs.chemrev.5b00736	journal	April 2016
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 Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Mark A. The Journal of Physical Chemistry A, Vol. 119, Issue 36 https://doi.org/10.1021/acs.jpca.5b04355	journal	July 2015
Picosecond Proton Transfer Kinetics in Water Revealed with Ultrafast IR Spectroscopy Carpenter, William B.; Fournier, Joseph A.; Lewis, Nicholas H. C. The Journal of Physical Chemistry B, Vol. 122, Issue 10 https://doi.org/10.1021/acs.jpcb.8b00118	journal	February 2018
Decomposition of the Experimental Raman and Infrared Spectra of Acidic Water into Proton, Special Pair, and Counterion Contributions Daly, Clyde A.; Streacker, Louis M.; Sun, Yuchen The Journal of Physical Chemistry Letters, Vol. 8, Issue 21 https://doi.org/10.1021/acs.jpclett.7b02435	journal	October 2017
The Curious Case of the Hydrated Proton Knight, Chris; Voth, Gregory A. Accounts of Chemical Research, Vol. 45, Issue 1 https://doi.org/10.1021/ar200140h	journal	August 2011
Extremely high polarizability of hydrogen bonds Janoschek, R.; Weidemann, E. G.; Pfeiffer, H. Journal of the American Chemical Society, Vol. 94, Issue 7 https://doi.org/10.1021/ja00762a032	journal	April 1972
Isomer-Selective Detection of Hydrogen-Bond Vibrations in the Protonated Water Hexamer Heine, Nadja; Fagiani, Matias R.; Rossi, Mariana Journal of the American Chemical Society, Vol. 135, Issue 22 https://doi.org/10.1021/ja401359t	journal	May 2013
Unraveling Anharmonic Effects in the Vibrational Predissociation Spectra of H ₅ O ₂ ⁺ and Its Deuterated Analogues Guasco, Timothy L.; Johnson, Mark A.; McCoy, Anne B. The Journal of Physical Chemistry A, Vol. 115, Issue 23 https://doi.org/10.1021/jp109999b	journal	June 2011
The Role of Quantum Effects on Structural and Electronic Fluctuations in Neat and Charged Water Giberti, Federico; Hassanali, Ali A.; Ceriotti, Michele The Journal of Physical Chemistry B, Vol. 118, Issue 46 https://doi.org/10.1021/jp507752e	journal	November 2014
Role of Charge Transfer in the Structure and Dynamics of the Hydrated Proton Swanson, Jessica M. J.; Simons, Jack The Journal of Physical Chemistry B, Vol. 113, Issue 15 https://doi.org/10.1021/jp810652v	journal	April 2009
Infrared Spectrum of the Hydrated Proton in Water Xu, Jianqing; Zhang, Yong; Voth, Gregory A. The Journal of Physical Chemistry Letters, Vol. 2, Issue 2 https://doi.org/10.1021/jz101536b	journal	December 2010
The nature of the hydrated excess proton in water Marx, Dominik; Tuckerman, Mark E.; Hutter, Jürg Nature, Vol. 397, Issue 6720 https://doi.org/10.1038/17579	journal	February 1999
A ‘clusters-in-liquid’ method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions Kulig, Waldemar; Agmon, Noam Nature Chemistry, Vol. 5, Issue 1 https://doi.org/10.1038/nchem.1503	journal	November 2012
The unique nature of H ⁺ in water Stoyanov, Evgenii S.; Stoyanova, Irina V.; Reed, Christopher A. Chem. Sci., Vol. 2, Issue 3 https://doi.org/10.1039/C0SC00415D	journal	January 2011
Calculated frequencies and intensities associated with coupling of the proton motion with the hydrogen bond stretching vibration in a double minimum potential surface Janoschek, R.; Weidemann, Erich G.; Zundel, Georg Journal of the Chemical Society, Faraday Transactions 2, Vol. 69 https://doi.org/10.1039/f29736900505	journal	January 1973
The vibrational spectrum of the hydrated proton: Comparison of experiment, simulation, and normal mode analysis Kim, Jeongho; Schmitt, Udo W.; Gruetzmacher, Julie A. The Journal of Chemical Physics, Vol. 116, Issue 2 https://doi.org/10.1063/1.1423327	journal	January 2002
Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water dimer. II. Infrared spectrum and vibrational dynamics Vendrell, Oriol; Gatti, Fabien; Meyer, Hans-Dieter The Journal of Chemical Physics, Vol. 127, Issue 18 https://doi.org/10.1063/1.2787596	journal	November 2007
Molecular modeling and assignment of IR spectra of the hydrated excess proton in isotopically dilute water Biswas, Rajib; Carpenter, William; Voth, Gregory A. The Journal of Chemical Physics, Vol. 145, Issue 15 https://doi.org/10.1063/1.4964723	journal	October 2016
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 Yu, Qi; Bowman, Joel M. The Journal of Chemical Physics, Vol. 146, Issue 12 https://doi.org/10.1063/1.4979601	journal	March 2017
IR spectral assignments for the hydrated excess proton in liquid water Biswas, Rajib; Carpenter, William; Fournier, Joseph A. The Journal of Chemical Physics, Vol. 146, Issue 15 https://doi.org/10.1063/1.4980121	journal	April 2017
Delocalization and stretch-bend mixing of the HOH bend in liquid water Carpenter, William B.; Fournier, Joseph A.; Biswas, Rajib The Journal of Chemical Physics, Vol. 147, Issue 8 https://doi.org/10.1063/1.4987153	journal	August 2017
Self-dissociation and protonic charge transport in water and Eigen, Manfred; De Maeyer, L. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 247, Issue 1251, p. 505-533 https://doi.org/10.1098/rspa.1958.0208	journal	October 1958
Concerted Hydrogen-Bond Dynamics in the Transport Mechanism of the Hydrated Proton: A First-Principles Molecular Dynamics Study Berkelbach, Timothy C.; Lee, Hee-Seung; Tuckerman, Mark E. Physical Review Letters, Vol. 103, Issue 23 https://doi.org/10.1103/PhysRevLett.103.238302	journal	November 2009
Gas-Phase Infrared Spectrum of the Protonated Water Dimer Asmis, K. R. Science, Vol. 299, Issue 5611 https://doi.org/10.1126/science.1081634	journal	February 2003
Spectral Signatures of Hydrated Proton Vibrations in Water Clusters Headrick, J. M. Science, Vol. 308, Issue 5729 https://doi.org/10.1126/science.1113094	journal	June 2005
Ultrafast 2D IR spectroscopy of the excess proton in liquid water Thämer, Martin; De Marco, Luigi; Ramasesha, Krupa Science, Vol. 350, Issue 6256 https://doi.org/10.1126/science.aab3908	journal	October 2015
Spectroscopic snapshots of the proton-transfer mechanism in water Wolke, C. T.; Fournier, J. A.; Dzugan, L. C. Science, Vol. 354, Issue 6316 https://doi.org/10.1126/science.aaf8425	journal	December 2016
Large-amplitude transfer motion of hydrated excess protons mapped by ultrafast 2D IR spectroscopy Dahms, Fabian; Fingerhut, Benjamin P.; Nibbering, Erik T. J. Science, Vol. 357, Issue 6350 https://doi.org/10.1126/science.aan5144	journal	July 2017
Source for ultrafast continuum infrared and terahertz radiation Petersen, Poul B.; Tokmakoff, Andrei Optics Letters, Vol. 35, Issue 12 https://doi.org/10.1364/OL.35.001962	journal	January 2010
Über den Zustand des Protons (Hydroniumions) in wäßriger Lösung* Wicke, E.; Eigen, M.; Ackermann, Th. Zeitschrift für Physikalische Chemie, Vol. 1, Issue 5_6 https://doi.org/10.1524/zpch.1954.1.5_6.340	journal	June 1954
Energiebänder der tunnelnden Überschuß-Protonen in flüssigen Säuren. Eine IR-spektroskopische Untersuchung der Natur der Gruppierungen H ₅ O ₂ ⁺ Zundel, G.; Metzger, H. Zeitschrift für Physikalische Chemie, Vol. 58, Issue 5_6 https://doi.org/10.1524/zpch.1968.58.5_6.225	journal	April 1968
Full dimensional (15D) quantum-dynamical simulation of the protonated water-dimer II: infrared spectrum and vibrational dynamics Vendrell, Oriol; Gatti, Fabien; Meyer, Hans-Dieter arXiv https://doi.org/10.48550/arxiv.0707.1004	text	January 2007

Cited By (13)

Tracking Aqueous Proton Transfer by Two-Dimensional Infrared Spectroscopy and ab Initio Molecular Dynamics Simulations Yuan, Rongfeng; Napoli, Joseph A.; Yan, Chang ACS Central Science, Vol. 5, Issue 7 https://doi.org/10.1021/acscentsci.9b00447	journal	May 2019
Hydrated Excess Proton Raman Spectral Densities Probed in Floating Water Bridges Teschke, Omar; Roberto de Castro, Jose; Valente Filho, Juracyr Ferraz ACS Omega, Vol. 3, Issue 10 https://doi.org/10.1021/acsomega.8b02285	journal	October 2018
Nature of Excess Hydrated Proton at the Water–Air Interface Das, Sudipta; Imoto, Sho; Sun, Shumei Journal of the American Chemical Society, Vol. 142, Issue 2 https://doi.org/10.1021/jacs.9b10807	journal	December 2019
Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H‐Bonding Liquid Observed by Transient 2D‐IR Spectroscopy Dereka, Bogdan; Helbing, Jan; Vauthey, Eric Angewandte Chemie, Vol. 130, Issue 52 https://doi.org/10.1002/ange.201808324	journal	November 2018
Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H-Bonding Liquid Observed by Transient 2D-IR Spectroscopy Dereka, Bogdan; Helbing, Jan; Vauthey, Eric Angewandte Chemie International Edition, Vol. 57, Issue 52 https://doi.org/10.1002/anie.201808324	journal	November 2018
Introduction Sun, Chang Q. Springer Series in Chemical Physics https://doi.org/10.1007/978-981-13-8441-7_1	book	January 2019
Lewis Acidic Solutions: H↔H Fragilization Sun, Chang Q. Springer Series in Chemical Physics https://doi.org/10.1007/978-981-13-8441-7_4	book	January 2019
Identifying Eigen-like hydrated protons at negatively charged interfaces Tyrode, Eric; Sengupta, Sanghamitra; Sthoer, Adrien Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-14370-5	journal	January 2020
Unprecedented O:⇔:O compression and H↔H fragilization in Lewis solutions Sun, Chang Q. Physical Chemistry Chemical Physics, Vol. 21, Issue 5 https://doi.org/10.1039/c8cp06910g	journal	January 2019
The solvation effect on the rattling behaviour of the hydrated excess proton in water Dong, Shaonan; Bi, Shuping Physical Chemistry Chemical Physics, Vol. 21, Issue 40 https://doi.org/10.1039/c9cp03827b	journal	January 2019
Entropic barriers in the kinetics of aqueous proton transfer Carpenter, William B.; Lewis, Nicholas H. C.; Fournier, Joseph A. The Journal of Chemical Physics, Vol. 151, Issue 3 https://doi.org/10.1063/1.5108907	journal	July 2019
Aqueous charge injection: solvation bonding dynamics, molecular nonbond interactions, and extraordinary solute capabilities Sun, Chang Q. International Reviews in Physical Chemistry, Vol. 37, Issue 3-4 https://doi.org/10.1080/0144235x.2018.1544446	journal	October 2018
Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H-Bonding Liquid Observed by Transient 2D-IR Spectroscopy Dereka, Bogdan; Helbing, Jan; Vauthey, Eric Wiley-VCH Verlag https://doi.org/10.5167/uzh-157856	text	January 2018

Similar Records

Decoding the 2D IR spectrum of the aqueous proton with high-level VSCF/VCI calculations

Journal Article · Tue Sep 22 20:00:00 EDT 2020 · Journal of Chemical Physics · OSTI ID:1761055

Picosecond Proton Transfer Kinetics in Water Revealed with Ultrafast IR Spectroscopy

Journal Article · Thu Feb 15 19:00:00 EST 2018 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry · OSTI ID:1539197

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY