Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21
Abstract
The spectroscopic features of protonated water species in dilute acid solutions have been long sought after for understanding the microscopic behavior of the proton in water with gas-phase water clusters H+(H2O)n extensively studied as bottom-up model systems. We present a new protocol for the calculation of the infrared (IR) spectra of complex systems, which combines the fragment-based Coupled Cluster method and anharmonic vibrational quasi-degenerate perturbation theory, and demonstrate its accuracy towards the complete and accurate assignment of the IR spectrum of the H+(H2O)21 cluster. The site-specific IR spectral signatures reveal two distinct structures for the internal and surface four-coordinated water molecules, which are ice-like and liquid-like, respectively. The effect of inter-molecular interaction between water molecules is addressed, and the vibrational resonance is found between the O-H stretching fundamental and the bending overtone of the nearest neighboring water molecule. The revelation of the spectral signature of the excess proton offers deeper insight into the nature of charge accommodation in the extended hydrogen-bonding network underpinning this aqueous cluster.
- Authors:
-
[1];
[3];
[4];
[5];
[6]
- China Pharmaceutical Univ., Nanjing (China); East China Normal Univ., Shanghai (China). Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development
- East China Normal Univ., Shanghai (China). Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development
- Univ. of Nebraska, Lincoln, NE (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA
- RIKEN, Saitama (Japan). Theoretical Molecular Science Laboratory
- East China Normal Univ., Shanghai (China). Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development; New York Univ. Shanghai (China). New York University-East China Normal University Center for Computational Chemistry
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences; National Natural Science Foundation of China (NSFC); National Key Research and Development Program of China; Shanghai Municipal Natural Science Foundation; Fundamental Research Funds for China Pharmaceutical University; JSPS KAKENHI
- OSTI Identifier:
- 1830221
- Report Number(s):
- PNNL-SA-163212
Journal ID: ISSN 2041-1723
- Grant/Contract Number:
- AC05-76RL01830; AC02-05CH11231; 21703289; 21922301; 21761132022; 21673074; 2016YFA0501700; 2019YFA090402; 2019YFA0905201; 18ZR1412600; 2632019FY01; 20H02701
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Computational chemistry; Quantum chemistry
Citation Formats
Liu, Jinfeng, Yang, Jinrong, Zeng, Xiao Cheng, Xantheas, Sotiris S., Yagi, Kiyoshi, and He, Xiao. Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21. United States: N. p., 2021.
Web. doi:10.1038/s41467-021-26284-x.
Liu, Jinfeng, Yang, Jinrong, Zeng, Xiao Cheng, Xantheas, Sotiris S., Yagi, Kiyoshi, & He, Xiao. Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21. United States. https://doi.org/10.1038/s41467-021-26284-x
Liu, Jinfeng, Yang, Jinrong, Zeng, Xiao Cheng, Xantheas, Sotiris S., Yagi, Kiyoshi, and He, Xiao. Fri .
"Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21". United States. https://doi.org/10.1038/s41467-021-26284-x. https://www.osti.gov/servlets/purl/1830221.
@article{osti_1830221,
title = {Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21},
author = {Liu, Jinfeng and Yang, Jinrong and Zeng, Xiao Cheng and Xantheas, Sotiris S. and Yagi, Kiyoshi and He, Xiao},
abstractNote = {The spectroscopic features of protonated water species in dilute acid solutions have been long sought after for understanding the microscopic behavior of the proton in water with gas-phase water clusters H+(H2O)n extensively studied as bottom-up model systems. We present a new protocol for the calculation of the infrared (IR) spectra of complex systems, which combines the fragment-based Coupled Cluster method and anharmonic vibrational quasi-degenerate perturbation theory, and demonstrate its accuracy towards the complete and accurate assignment of the IR spectrum of the H+(H2O)21 cluster. The site-specific IR spectral signatures reveal two distinct structures for the internal and surface four-coordinated water molecules, which are ice-like and liquid-like, respectively. The effect of inter-molecular interaction between water molecules is addressed, and the vibrational resonance is found between the O-H stretching fundamental and the bending overtone of the nearest neighboring water molecule. The revelation of the spectral signature of the excess proton offers deeper insight into the nature of charge accommodation in the extended hydrogen-bonding network underpinning this aqueous cluster.},
doi = {10.1038/s41467-021-26284-x},
journal = {Nature Communications},
number = 1,
volume = 12,
place = {United States},
year = {Fri Oct 22 00:00:00 EDT 2021},
month = {Fri Oct 22 00:00:00 EDT 2021}
}
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Works referenced in this record:
Site-specific vibrational spectral signatures of water molecules in the magic H 3 O + (H 2 O) 20 and Cs + (H 2 O) 20 clusters
journal, December 2014
- Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 51
Capturing intrinsic site-dependent spectral signatures and lifetimes of isolated OH oscillators in extended water networks
journal, November 2019
- Yang, Nan; Duong, Chinh H.; Kelleher, Patrick J.
- Nature Chemistry, Vol. 12, Issue 2
Ultrafast Dynamics of Liquid Water: Energy Relaxation and Transfer Processes of the OH Stretch and the HOH Bend
journal, June 2015
- Imoto, Sho; Xantheas, Sotiris S.; Saito, Shinji
- The Journal of Physical Chemistry B, Vol. 119, Issue 34
Vibrational quasi-degenerate perturbation theory: applications to fermi resonance in CO2, H2CO, and C6H6
journal, January 2008
- Yagi, Kiyoshi; Hirata, So; Hirao, Kimihiko
- Physical Chemistry Chemical Physics, Vol. 10, Issue 13
Both Zundel and Eigen Isomers Contribute to the IR Spectrum of the Gas-Phase H 9 O 4 + Cluster
journal, December 2013
- Kulig, Waldemar; Agmon, Noam
- The Journal of Physical Chemistry B, Vol. 118, Issue 1
Second-order many-body perturbation study of ice Ih
journal, November 2012
- He, Xiao; Sode, Olaseni; Xantheas, Sotiris S.
- The Journal of Chemical Physics, Vol. 137, Issue 20
Interfacial Structures of Acidic and Basic Aqueous Solutions
journal, October 2008
- Tian, Chuanshan; Ji, Na; Waychunas, Glenn A.
- Journal of the American Chemical Society, Vol. 130, Issue 39
Anharmonic Vibrational Calculations Based on Group-Localized Coordinates: Applications to Internal Water Molecules in Bacteriorhodopsin
journal, July 2021
- Yagi, Kiyoshi; Sugita, Yuji
- Journal of Chemical Theory and Computation, Vol. 17, Issue 8
Tag-Free and Isotopomer-Selective Vibrational Spectroscopy of the Cryogenically Cooled H 9 O 4 + Cation with Two-Color, IR–IR Double-Resonance Photoexcitation: Isolating the Spectral Signature of a Single OH Group in the Hydronium Ion Core
journal, October 2018
- Duong, Chinh H.; Yang, Nan; Kelleher, Patrick J.
- The Journal of Physical Chemistry A, Vol. 122, Issue 48
Deciphering the infrared spectrum of the protonated water pentamer and the hybrid Eigen–Zundel cation
journal, January 2014
- Kulig, Waldemar; Agmon, Noam
- Physical Chemistry Chemical Physics, Vol. 16, Issue 10
Ab initio vibrational state calculations with a quartic force field: Applications to H2CO, C2H4, CH3OH, CH3CCH, and C6H6
journal, July 2004
- Yagi, Kiyoshi; Hirao, Kimihiko; Taketsugu, Tetsuya
- The Journal of Chemical Physics, Vol. 121, Issue 3
Ultrafast 2D IR spectroscopy of the excess proton in liquid water
journal, October 2015
- Thämer, Martin; De Marco, Luigi; Ramasesha, Krupa
- Science, Vol. 350, Issue 6256
Infrared Signature of Structures Associated with the H+(H2O)n (n = 6 to 27) Clusters
journal, May 2004
- Shin, J. -W.
- Science, Vol. 304, Issue 5674
The nature of the hydrated excess proton in water
journal, February 1999
- Marx, Dominik; Tuckerman, Mark E.; Hutter, Jürg
- Nature, Vol. 397, Issue 6720
An analysis of hydrated proton diffusion in ab initio molecular dynamics
journal, January 2015
- Tse, Ying-Lung Steve; Knight, Chris; Voth, Gregory A.
- The Journal of Chemical Physics, Vol. 142, Issue 1
Infrared Spectra and Hydrogen-Bonded Network Structures of Large Protonated Water Clusters H+(H2O)n (n=20-200)
journal, November 2010
- Mizuse, Kenta; Mikami, Naohiko; Fujii, Asuka
- Angewandte Chemie International Edition, Vol. 49, Issue 52
Benchmark Electronic Structure Calculations for H 3 O + (H 2 O) n , n = 0–5, Clusters and Tests of an Existing 1,2,3-Body Potential Energy Surface with a New 4-Body Correction
journal, August 2018
- Heindel, Joseph P.; Yu, Qi; Bowman, Joel M.
- Journal of Chemical Theory and Computation, Vol. 14, Issue 9
Vibrational quasi-degenerate perturbation theory with optimized coordinates: Applications to ethylene and trans -1,3-butadiene
journal, February 2014
- Yagi, Kiyoshi; Otaki, Hiroki
- The Journal of Chemical Physics, Vol. 140, Issue 8
Infrared Spectra of Protonated Water Clusters, H + (H 2 O) 4 , in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory
journal, March 2017
- Yagi, Kiyoshi; Thomsen, Bo
- The Journal of Physical Chemistry A, Vol. 121, Issue 12
Electrostatically Embedded Many-Body Correlation Energy, with Applications to the Calculation of Accurate Second-Order Møller−Plesset Perturbation Theory Energies for Large Water Clusters
journal, May 2007
- Dahlke, Erin E.; Truhlar, Donald G.
- Journal of Chemical Theory and Computation, Vol. 3, Issue 4
Clustering of water on hydrated protons in a supersonic free jet expansion
journal, December 1974
- Searcy, J. Q.; Fenn, J. B.
- The Journal of Chemical Physics, Vol. 61, Issue 12
Energy-Based Molecular Fragmentation Methods
journal, April 2015
- Collins, Michael A.; Bettens, Ryan P. A.
- Chemical Reviews, Vol. 115, Issue 12
Structural Origin of the Antimagic Number in Protonated Water Clusters H + (H 2 O) n : Spectroscopic Observation of the “Missing” Water Molecule in the Outermost Hydration Shell
journal, August 2011
- Mizuse, Kenta; Fujii, Asuka
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 17
Reinvestigation of the Infrared Spectrum of the Gas-Phase Protonated Water Tetramer
journal, April 2017
- Wang, Huan; Agmon, Noam
- The Journal of Physical Chemistry A, Vol. 121, Issue 16
Flexible simple point-charge water model with improved liquid-state properties
journal, January 2006
- Wu, Yujie; Tepper, Harald L.; Voth, Gregory A.
- The Journal of Chemical Physics, Vol. 124, Issue 2
Spectral Signatures of Hydrated Proton Vibrations in Water Clusters
journal, June 2005
- Headrick, J. M.
- Science, Vol. 308, Issue 5729
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
Infrared Spectroscopic Evidence for Protonated Water Clusters Forming Nanoscale Cages
journal, May 2004
- Miyazaki, M.
- Science, Vol. 304, Issue 5674
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
- Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Mark A.
- The Journal of Physical Chemistry A, Vol. 119, Issue 36
Ab initio studies of (H2O)20H+ and (H2O)21H+ prismic, fused cubic and dodecahedral clusters: can H3O+ ion remain in cage cavity?
journal, March 2000
- Khan, Arshad
- Chemical Physics Letters, Vol. 319, Issue 5-6
Gas-Phase Infrared Spectrum of the Protonated Water Dimer
journal, February 2003
- Asmis, K. R.
- Science, Vol. 299, Issue 5611
Probing the Ion-Specific Effects at the Water/Air Interface and Water-Mediated Ion Pairing in Sodium Halide Solution with Ab Initio Molecular Dynamics
journal, October 2018
- Liu, Jinfeng; Zhang, John Z. H.; He, Xiao
- The Journal of Physical Chemistry B, Vol. 122, Issue 44
Delocalization of Protons in Liquid Water
journal, July 2002
- Bakker, H. J.
- Science, Vol. 297, Issue 5581
The structure and vibrational spectra of proton hydrates: as a simplest stable ion
journal, July 2009
- Vener, M. V.; Librovich, N. B.
- International Reviews in Physical Chemistry, Vol. 28, Issue 3
Proton Transfer, Acid-Base Catalysis, and Enzymatic Hydrolysis. Part I: ELEMENTARY PROCESSES
journal, January 1964
- Eigen, M.
- Angewandte Chemie International Edition in English, Vol. 3, Issue 1
Electrostatically Embedded Many-Body Expansion for Large Systems, with Applications to Water Clusters
journal, November 2006
- Dahlke, Erin E.; Truhlar, Donald G.
- Journal of Chemical Theory and Computation, Vol. 3, Issue 1
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
Tracking Hydronium/Water Stretches in Magic H 3 O + (H 2 O) 20 Clusters through High-level Quantum VSCF/VCI Calculations
journal, January 2020
- Yu, Qi; Bowman, Joel M.
- The Journal of Physical Chemistry A, Vol. 124, Issue 6
Multiresolution potential energy surfaces for vibrational state calculations
journal, July 2007
- Yagi, Kiyoshi; Hirata, So; Hirao, Kimihiko
- Theoretical Chemistry Accounts, Vol. 118, Issue 3
Global minima of protonated water clusters
journal, July 2000
- Hodges, Matthew P.; Wales, David J.
- Chemical Physics Letters, Vol. 324, Issue 4
Permutationally Invariant Potential Energy Surfaces
journal, April 2018
- Qu, Chen; Yu, Qi; Bowman, Joel M.
- Annual Review of Physical Chemistry, Vol. 69, Issue 1
Infrared Spectra of Ices Ih and Ic in the Range 4000 to 350 cm —1
journal, March 1964
- Bertie, J. E.; Whalley, E.
- The Journal of Chemical Physics, Vol. 40, Issue 6
Anharmonicity and the Eigen-Zundel Dilemma in the IR Spectrum of the Protonated 21 Water Cluster
journal, December 2010
- Torrent-Sucarrat, Miquel; Anglada, Josep M.
- Journal of Chemical Theory and Computation, Vol. 7, Issue 2
Direct vibrational self-consistent field method: Applications to H2O and H2CO
journal, July 2000
- Yagi, Kiyoshi; Taketsugu, Tetsuya; Hirao, Kimihiko
- The Journal of Chemical Physics, Vol. 113, Issue 3
Fragment-based quantum mechanical approach to biomolecules, molecular clusters, molecular crystals and liquids
journal, January 2020
- Liu, Jinfeng; He, Xiao
- Physical Chemistry Chemical Physics, Vol. 22, Issue 22
Infrared spectroscopic studies on hydrogen-bonded water networks in gas phase clusters
journal, June 2013
- Fujii, Asuka; Mizuse, Kenta
- International Reviews in Physical Chemistry, Vol. 32, Issue 2
Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster
journal, May 2014
- Fournier, J. A.; Johnson, C. J.; Wolke, C. T.
- Science, Vol. 344, Issue 6187
On the coupling strength in potential energy surfaces for vibrational calculations
journal, November 2009
- Seidler, Peter; Kaga, Tatsuya; Yagi, Kiyoshi
- Chemical Physics Letters, Vol. 483, Issue 1-3
High-Level Quantum Calculations of the IR Spectra of the Eigen, Zundel, and Ring Isomers of H + (H 2 O) 4 Find a Single Match to Experiment
journal, August 2017
- Yu, Qi; Bowman, Joel M.
- Journal of the American Chemical Society, Vol. 139, Issue 32
Spying on the neighbors' pool
journal, December 2016
- Xantheas, Sotiris S.
- Science, Vol. 354, Issue 6316
Fragmentation Methods: A Route to Accurate Calculations on Large Systems
journal, August 2011
- Gordon, Mark S.; Fedorov, Dmitri G.; Pruitt, Spencer R.
- Chemical Reviews, Vol. 112, Issue 1
Stability, Vibrations, and Diffusion of Hydrogen Gas in Clathrate Hydrates: Insights from Ab Initio Calculations on Condensed-Phase Crystalline Structures
journal, April 2019
- Lu, Qiangna; He, Xiao; Hu, Wenxin
- The Journal of Physical Chemistry C, Vol. 123, Issue 19
Spectroscopic snapshots of the proton-transfer mechanism in water
journal, December 2016
- Wolke, C. T.; Fournier, J. A.; Dzugan, L. C.
- Science, Vol. 354, Issue 6316
Infrared Intensities of Liquids XX: The Intensity of the OH Stretching Band of Liquid Water Revisited, and the Best Current Values of the Optical Constants of H 2 O(l) at 25°C between 15,000 and 1 cm −1
journal, August 1996
- Bertie, John E.; Lan, Zhida
- Applied Spectroscopy, Vol. 50, Issue 8
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
The properties of ion-water clusters. I. The protonated 21-water cluster
journal, August 2005
- Iyengar, Srinivasan S.; Petersen, Matt K.; Day, Tyler J. F.
- The Journal of Chemical Physics, Vol. 123, Issue 8
Dances with hydrogen cations
journal, February 2009
- Xantheas, Sotiris S.
- Nature, Vol. 457, Issue 7230
Fragment Quantum Mechanical Method for Large-Sized Ion–Water Clusters
journal, April 2017
- Liu, Jinfeng; Qi, Lian-Wen; Zhang, John Z. H.
- Journal of Chemical Theory and Computation, Vol. 13, Issue 5
Flexible, ab initio potential, and dipole moment surfaces for water. I. Tests and applications for clusters up to the 22-mer
journal, March 2011
- Wang, Yimin; Huang, Xinchuan; Shepler, Benjamin C.
- The Journal of Chemical Physics, Vol. 134, Issue 9
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