Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21

Journal Article · · Nature Communications
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]
  1. China Pharmaceutical Univ., Nanjing (China); East China Normal Univ., Shanghai (China). Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development
  2. East China Normal Univ., Shanghai (China). Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development
  3. Univ. of Nebraska, Lincoln, NE (United States)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA
  5. RIKEN, Saitama (Japan). Theoretical Molecular Science Laboratory
  6. 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
+ Show Author Affiliations

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.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences; National Natural Science Foundation of China (NSFC); National Key R&D Program of China; Shanghai Municipal Natural Science Foundation; Fundamental Research Funds for China Pharmaceutical University; JSPS KAKENHI
Grant/Contract Number:
AC05-76RL01830; AC02-05CH11231
OSTI ID:
1830221
Report Number(s):
PNNL-SA--163212
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 12; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (65)

Flexible simple point-charge water model with improved liquid-state properties journal January 2006
Fragment Quantum Mechanical Method for Large-Sized Ion–Water Clusters journal April 2017
Gas-Phase Infrared Spectrum of the Protonated Water Dimer journal February 2003
Vibrational predissociation spectra and hydrogen-bond topologies of H + (H 2 O) 9–11 journal January 2005
Spectral Signatures of Hydrated Proton Vibrations in Water Clusters journal June 2005
Infrared spectroscopic studies on hydrogen-bonded water networks in gas phase clusters journal June 2013
Tracking Hydronium/Water Stretches in Magic H 3 O + (H 2 O) 20 Clusters through High-level Quantum VSCF/VCI Calculations journal January 2020
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
Spectroscopic snapshots of the proton-transfer mechanism in water journal December 2016
Special Pair Dance and Partner Selection: Elementary Steps in Proton Transport in Liquid Water journal August 2008
Proton Transfer, Acid-Base Catalysis, and Enzymatic Hydrolysis. Part I: ELEMENTARY PROCESSES journal January 1964
Flexible, ab initio potential, and dipole moment surfaces for water. I. Tests and applications for clusters up to the 22-mer journal March 2011
Anharmonic Vibrational Calculations Based on Group-Localized Coordinates: Applications to Internal Water Molecules in Bacteriorhodopsin journal July 2021
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
Global minima of protonated water clusters journal July 2000
Direct vibrational self-consistent field method: Applications to H2O and H2CO journal July 2000
On the coupling strength in potential energy surfaces for vibrational calculations journal November 2009
An analysis of hydrated proton diffusion in ab initio molecular dynamics journal January 2015
Vibrational quasi-degenerate perturbation theory with optimized coordinates: Applications to ethylene and trans -1,3-butadiene journal February 2014
Structure of liquid water – a dynamical mixture of tetrahedral and ‘ring-and-chain’ like structures journal January 2017
Energy-Based Molecular Fragmentation Methods journal April 2015
Interfacial Structures of Acidic and Basic Aqueous Solutions journal October 2008
Infrared Spectroscopic Evidence for Protonated Water Clusters Forming Nanoscale Cages journal May 2004
Deciphering the infrared spectrum of the protonated water pentamer and the hybrid Eigen–Zundel cation journal January 2014
Reinvestigation of the Infrared Spectrum of the Gas-Phase Protonated Water Tetramer journal April 2017
Delocalization of Protons in Liquid Water journal July 2002
Stability, Vibrations, and Diffusion of Hydrogen Gas in Clathrate Hydrates: Insights from Ab Initio Calculations on Condensed-Phase Crystalline Structures journal April 2019
Spying on the neighbors' pool journal December 2016
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
A ‘clusters-in-liquid’ method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions journal November 2012
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
Permutationally Invariant Potential Energy Surfaces journal April 2018
Vibrational quasi-degenerate perturbation theory: applications to fermi resonance in CO2, H2CO, and C6H6 journal January 2008
Accurate prediction of energetic properties of ionic liquid clusters using a fragment-based quantum mechanical method journal January 2017
Infrared Spectra of Ices Ih and Ic in the Range 4000 to 350 cm —1 journal March 1964
Dances with hydrogen cations journal February 2009
Ultrafast Dynamics of Liquid Water: Energy Relaxation and Transfer Processes of the OH Stretch and the HOH Bend journal June 2015
Ultrafast 2D IR spectroscopy of the excess proton in liquid water journal October 2015
Ab initio vibrational state calculations with a quartic force field: Applications to H2CO, C2H4, CH3OH, CH3CCH, and C6H6 journal July 2004
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
Second-order many-body perturbation study of ice Ih journal November 2012
Capturing intrinsic site-dependent spectral signatures and lifetimes of isolated OH oscillators in extended water networks journal November 2019
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
The structure and vibrational spectra of proton hydrates: as a simplest stable ion journal July 2009
The properties of ion-water clusters. I. The protonated 21-water cluster journal August 2005
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
Both Zundel and Eigen Isomers Contribute to the IR Spectrum of the Gas-Phase H 9 O 4 + Cluster journal December 2013
Clustering of water on hydrated protons in a supersonic free jet expansion journal December 1974
Fragmentation Methods: A Route to Accurate Calculations on Large Systems journal August 2011
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
Multiresolution potential energy surfaces for vibrational state calculations journal July 2007
The nature of the hydrated excess proton in water journal February 1999
Fragment-based quantum mechanical approach to biomolecules, molecular clusters, molecular crystals and liquids journal January 2020
Anharmonicity and the Eigen-Zundel Dilemma in the IR Spectrum of the Protonated 21 Water Cluster journal December 2010
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
Proton transfer through the water gossamer journal July 2013
Fragment quantum chemical approach to geometry optimization and vibrational spectrum calculation of proteins journal January 2016
Infrared Spectra and Hydrogen-Bonded Network Structures of Large Protonated Water Clusters H+(H2O)n (n=20-200) journal November 2010
Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster journal May 2014
Hydrogen-bond structure dynamics in bulk water: insights from ab initio simulations with coupled cluster theory journal January 2018
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
Infrared Signature of Structures Associated with the H+(H2O)n (n = 6 to 27) Clusters journal May 2004
Infrared Spectrum of the Hydrated Proton in Water journal December 2010
Electrostatically Embedded Many-Body Expansion for Large Systems, with Applications to Water Clusters journal November 2006
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

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Computational chemistry
Quantum chemistry