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

Title: 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

Abstract

Here, theoretical models of proton hydration with tens of water molecules indicate that the excess proton is embedded on the surface of clathrate-like cage structures with one or two water molecules in the interior. The evidence for these structures has been indirect, however, because the experimental spectra in the critical H-bonding region of the OH stretching vibrations have been too diffuse to provide band patterns that distinguish between candidate structures predicted theoretically. Here we exploit the slow cooling afforded by cryogenic ion trapping, along with isotopic substitution, to quench water clusters attached to the H3O+ and Cs+ ions into structures that yield well-resolved vibrational bands over the entire 215- to 3,800-cm-1 range. The magic H3O+(H2O)20 cluster yields particularly clear spectral signatures that can, with the aid of ab initio predictions, be traced to specific classes of network sites in the predicted pentagonal dodecahedron H-bonded cage with the hydronium ion residing on the surface.

Authors:
 [1];  [1];  [1];  [1];  [2];  [2];  [2];  [3];  [4];  [4];  [3]
+ Show Author Affiliations
  1. Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, CT 06520,
  2. Fritz-Haber-Institut der Max-Planck-Gesellschaft, D-14195 Berlin, Germany, and
  3. Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, D-04103 Leipzig, Germany
  4. Fritz-Haber-Institut der Max-Planck-Gesellschaft, D-14195 Berlin, Germany, and, Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, D-04103 Leipzig, Germany
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF); US Air Force; US Department of Defense (DOD)
OSTI Identifier:
1235099
Alternate Identifier(s):
OSTI ID: 1348391
Grant/Contract Number:  
FG02-06ER15800; CHE-1213634; FA9550-13-1-0007; CNS 08-21132
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 111 Journal Issue: 51; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cryogenic vibrational spectroscopy; hydrogen bonding; water clusters

Citation Formats

Fournier, Joseph A., Wolke, Conrad T., Johnson, Christopher J., Johnson, Mark A., Heine, Nadja, Gewinner, Sandy, Schöllkopf, Wieland, Esser, Tim K., Fagiani, Matias R., Knorke, Harald, and Asmis, Knut R. 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. United States: N. p., 2014. Web. doi:10.1073/pnas.1420734111.
Copy to clipboard
Fournier, Joseph A., Wolke, Conrad T., Johnson, Christopher J., Johnson, Mark A., Heine, Nadja, Gewinner, Sandy, Schöllkopf, Wieland, Esser, Tim K., Fagiani, Matias R., Knorke, Harald, & Asmis, Knut R. 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. United States. https://doi.org/10.1073/pnas.1420734111
Copy to clipboard
Fournier, Joseph A., Wolke, Conrad T., Johnson, Christopher J., Johnson, Mark A., Heine, Nadja, Gewinner, Sandy, Schöllkopf, Wieland, Esser, Tim K., Fagiani, Matias R., Knorke, Harald, and Asmis, Knut R. Mon . "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". United States. https://doi.org/10.1073/pnas.1420734111.
Copy to clipboard
@article{osti_1235099,
title = {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},
author = {Fournier, Joseph A. and Wolke, Conrad T. and Johnson, Christopher J. and Johnson, Mark A. and Heine, Nadja and Gewinner, Sandy and Schöllkopf, Wieland and Esser, Tim K. and Fagiani, Matias R. and Knorke, Harald and Asmis, Knut R.},
abstractNote = {Here, theoretical models of proton hydration with tens of water molecules indicate that the excess proton is embedded on the surface of clathrate-like cage structures with one or two water molecules in the interior. The evidence for these structures has been indirect, however, because the experimental spectra in the critical H-bonding region of the OH stretching vibrations have been too diffuse to provide band patterns that distinguish between candidate structures predicted theoretically. Here we exploit the slow cooling afforded by cryogenic ion trapping, along with isotopic substitution, to quench water clusters attached to the H3O+ and Cs+ ions into structures that yield well-resolved vibrational bands over the entire 215- to 3,800-cm-1 range. The magic H3O+(H2O)20 cluster yields particularly clear spectral signatures that can, with the aid of ab initio predictions, be traced to specific classes of network sites in the predicted pentagonal dodecahedron H-bonded cage with the hydronium ion residing on the surface.},
doi = {10.1073/pnas.1420734111},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 51,
volume = 111,
place = {United States},
year = {Mon Dec 08 00:00:00 EST 2014},
month = {Mon Dec 08 00:00:00 EST 2014}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1073/pnas.1420734111
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 54 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Messenger-Tagging Electrosprayed Ions: Vibrational Spectroscopy of Suberate Dianions
journal, May 2009

  • Goebbert, Daniel J.; Wende, Torsten; Bergmann, Risshu
  • The Journal of Physical Chemistry A, Vol. 113, Issue 20
  • DOI: 10.1021/jp809390x

Vibrational Spectroscopy as a Probe of Structure and Dynamics in Liquid Water
journal, March 2010

  • Bakker, H. J.; Skinner, J. L.
  • Chemical Reviews, Vol. 110, Issue 3
  • DOI: 10.1021/cr9001879

Formation and photodepletion of cluster ion–messenger atom complexes in a cold ion trap: Infrared spectroscopy of VO+, VO2+, and VO3+
journal, December 2003

  • Brümmer, Mathias; Kaposta, Cristina; Santambrogio, Gabriele
  • The Journal of Chemical Physics, Vol. 119, Issue 24
  • DOI: 10.1063/1.1634254

Vibrational predissociation spectroscopy of the H2-tagged mono- and dicarboxylate anions of dodecanedioic acid
journal, March 2011

  • Kamrath, Michael Z.; Relph, Rachael A.; Guasco, Timothy L.
  • International Journal of Mass Spectrometry, Vol. 300, Issue 2-3
  • DOI: 10.1016/j.ijms.2010.10.021

Spectroscopic studies of cold, gas-phase biomolecular ions
journal, July 2009

  • Rizzo, Thomas R.; Stearns, Jaime A.; Boyarkin, Oleg V.
  • International Reviews in Physical Chemistry, Vol. 28, Issue 3
  • DOI: 10.1080/01442350903069931

IR and Raman spectra of liquid water: Theory and interpretation
journal, June 2008

  • Auer, B. M.; Skinner, J. L.
  • The Journal of Chemical Physics, Vol. 128, Issue 22
  • DOI: 10.1063/1.2925258

Ultrafast Structural Dynamics of Water Induced by Dissipation of Vibrational Energy
journal, February 2007

  • Ashihara, Satoshi; Huse, Nils; Espagne, Agathe
  • The Journal of Physical Chemistry A, Vol. 111, Issue 5
  • DOI: 10.1021/jp0676538

Infrared Spectroscopy and Hydrogen-Bond Dynamics of Liquid Water from Centroid Molecular Dynamics with an Ab Initio-Based Force Field
journal, October 2009

  • Paesani, Francesco; Xantheas, Sotiris S.; Voth, Gregory A.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 39
  • DOI: 10.1021/jp907648y

Vibrational Spectroscopy of Microhydrated Conjugate Base Anions
journal, June 2011

  • Asmis, Knut R.; Neumark, Daniel M.
  • Accounts of Chemical Research, Vol. 45, Issue 1
  • DOI: 10.1021/ar2000748

Time Resolved Spectroscopy of Water in the Infrared: New Data and Discussion
journal, May 2002

  • Laenen, Robert; Simeonidis, Konstantinos; Laubereau, Alfred
  • Bulletin of the Chemical Society of Japan, Vol. 75, Issue 5
  • DOI: 10.1246/bcsj.75.925

Observation of H 2 Aggregation onto a Doubly Charged Anion in a Temperature-Controlled Ion Trap
journal, December 2008

  • Wang, Xue-Bin; Xing, Xiao-Peng; Wang, Lai-Sheng
  • The Journal of Physical Chemistry A, Vol. 112, Issue 51
  • DOI: 10.1021/jp808769m

Hydrated Alkali Metal Ions: Spectroscopic Evidence for Clathrates
journal, July 2013

  • Cooper, Richard J.; Chang, Terrence M.; Williams, Evan R.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 30
  • DOI: 10.1021/jp405147h

Slow Photoelectron Velocity-Map Imaging Spectroscopy of Cold Thiozonide (S 3 – )
journal, March 2013

  • Kim, Jongjin B.; Hock, Christian; Yacovitch, Tara I.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 34
  • DOI: 10.1021/jp401083u

Ultrafast Vibrational Population Dynamics of Water and Related Systems:  A Theoretical Perspective
journal, April 2004

  • Rey, Rossend; Møller, Klaus B.; Hynes, James T.
  • Chemical Reviews, Vol. 104, Issue 4
  • DOI: 10.1021/cr020675f

Cryogenic Ion Chemistry and Spectroscopy
journal, August 2013

  • Wolk, Arron B.; Leavitt, Christopher M.; Garand, Etienne
  • Accounts of Chemical Research, Vol. 47, Issue 1
  • DOI: 10.1021/ar400125a

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

Structural information on alkali cation microhydration clusters from infrared spectra
journal, January 2003

  • Schulz, Franziska; Hartke, Bernd
  • Physical Chemistry Chemical Physics, Vol. 5, Issue 22
  • DOI: 10.1039/b310657h

Multidimensional infrared spectroscopy of water. I. Vibrational dynamics in two-dimensional IR line shapes
journal, November 2006

  • Loparo, Joseph J.; Roberts, Sean T.; Tokmakoff, Andrei
  • The Journal of Chemical Physics, Vol. 125, Issue 19
  • DOI: 10.1063/1.2382895

Infrared spectra of the cluster ions H 7 O + 3 ⋅H 2 and H 9 O + 4 ⋅H 2
journal, August 1986

  • Okumura, M.; Yeh, L. I.; Myers, J. D.
  • The Journal of Chemical Physics, Vol. 85, Issue 4
  • DOI: 10.1063/1.451079

Multidimensional infrared spectroscopy of water. II. Hydrogen bond switching dynamics
journal, November 2006

  • Loparo, Joseph J.; Roberts, Sean T.; Tokmakoff, Andrei
  • The Journal of Chemical Physics, Vol. 125, Issue 19
  • DOI: 10.1063/1.2382896

Experimental Evidence of Fermi Resonances in Isotopically Dilute Water from Ultrafast Broadband IR Spectroscopy
journal, May 2013

  • De Marco, Luigi; Ramasesha, Krupa; Tokmakoff, Andrei
  • The Journal of Physical Chemistry B, Vol. 117, Issue 49
  • DOI: 10.1021/jp4034613

Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster
journal, May 2014

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

  • Heine, Nadja; Fagiani, Matias R.; Rossi, Mariana
  • Journal of the American Chemical Society, Vol. 135, Issue 22
  • DOI: 10.1021/ja401359t

A pulsed supersonic entrainment reactor for the rational preparation of cold ionic complexes
journal, January 2000

  • Robertson, W. H.; Kelley, J. A.; Johnson, M. A.
  • Review of Scientific Instruments, Vol. 71, Issue 12
  • DOI: 10.1063/1.1326931

Computer simulations of cesium–water clusters: Do ion–water clusters form gas‐phase clathrates?
journal, November 1994

  • Smith, David E.; Dang, Liem X.
  • The Journal of Chemical Physics, Vol. 101, Issue 9
  • DOI: 10.1063/1.468213

Hydrogen bonding and Raman, IR, and 2D-IR spectroscopy of dilute HOD in liquid D2O
journal, June 2007

  • Auer, B.; Kumar, R.; Schmidt, J. R.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 36
  • DOI: 10.1073/pnas.0701482104

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

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
  • DOI: 10.1063/1.2007628

Ultrafast memory loss and energy redistribution in the hydrogen bond network of liquid H2O
journal, March 2005

The Curious Case of the Hydrated Proton
journal, August 2011

  • Knight, Chris; Voth, Gregory A.
  • Accounts of Chemical Research, Vol. 45, Issue 1
  • DOI: 10.1021/ar200140h
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: