Isotopomer-selective spectra of a single intact H2O molecule in the Cs+(D2O)5H2O isotopologue: Going beyond pattern recognition to harvest the structural information encoded in vibrational spectra
Abstract
We report the vibrational signatures of a single H2O water molecule occupying distinct sites of the hydration network in the Cs+(H2O)6 cluster. This is accomplished using isotopomer selective IR-IR hole-burning on the Cs+(D2O)5(H2O) clusters formed by gas-phase exchange of a single, intact H2O molecule for D2O in the Cs+(D2O)6 ion. The OH stretching pattern of the Cs+(H2O)6 isotopologue is accurately recovered by superposition of the isotopomer spectra, thus establishing that the H2O incorporation is random and that the OH stretching manifold is largely due to contributions from decoupled water molecules. This behavior enables a powerful new way to extract structural information from vibrational spectra of size-selected clusters by explicitly identifying the local environments responsible for specific infrared features. The Cs+(H2O)6 structure was unambiguously assigned to the 4.1.1 isomer (a homodromic water tetramer with two additional flanking water molecules) from the fact that its computed IR spectrum matches the observed overall pattern and recovers the embedded correlations in the two OH stretching bands of the water molecule in the Cs+(D2O)5(H2O) isotopomers. The 4.1.1 isomer is the lowest in energy among other candidate networks at advanced (e.g., CCSD(T)) levels of theoretical treatment after corrections for (anharmonic) zero-point energy (ZPE). With the structuremore »
- Authors:
-
- Yale Univ., New Haven, CT (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- 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, and Biosciences Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1243220
- Alternate Identifier(s):
- OSTI ID: 1238206
- Report Number(s):
- PNNL-SA-114570
Journal ID: ISSN 0021-9606; JCPSA6; KC0301050
- Grant/Contract Number:
- AC05-76RL01830; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 7; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Isomerism; Lasers; Artificial intelligence; Nonlinear optics; Zero point energy; Isotopomers; Coupled-cluster methods; Vibrational spectra; Gas phase; Ion sources
Citation Formats
Wolke, Conrad T., Fournier, Joseph A., Miliordos, Evangelos, Kathmann, Shawn M., Xantheas, Sotiris S., and Johnson, Mark A. Isotopomer-selective spectra of a single intact H2O molecule in the Cs+(D2O)5H2O isotopologue: Going beyond pattern recognition to harvest the structural information encoded in vibrational spectra. United States: N. p., 2016.
Web. doi:10.1063/1.4941285.
Wolke, Conrad T., Fournier, Joseph A., Miliordos, Evangelos, Kathmann, Shawn M., Xantheas, Sotiris S., & Johnson, Mark A. Isotopomer-selective spectra of a single intact H2O molecule in the Cs+(D2O)5H2O isotopologue: Going beyond pattern recognition to harvest the structural information encoded in vibrational spectra. United States. https://doi.org/10.1063/1.4941285
Wolke, Conrad T., Fournier, Joseph A., Miliordos, Evangelos, Kathmann, Shawn M., Xantheas, Sotiris S., and Johnson, Mark A. Wed .
"Isotopomer-selective spectra of a single intact H2O molecule in the Cs+(D2O)5H2O isotopologue: Going beyond pattern recognition to harvest the structural information encoded in vibrational spectra". United States. https://doi.org/10.1063/1.4941285. https://www.osti.gov/servlets/purl/1243220.
@article{osti_1243220,
title = {Isotopomer-selective spectra of a single intact H2O molecule in the Cs+(D2O)5H2O isotopologue: Going beyond pattern recognition to harvest the structural information encoded in vibrational spectra},
author = {Wolke, Conrad T. and Fournier, Joseph A. and Miliordos, Evangelos and Kathmann, Shawn M. and Xantheas, Sotiris S. and Johnson, Mark A.},
abstractNote = {We report the vibrational signatures of a single H2O water molecule occupying distinct sites of the hydration network in the Cs+(H2O)6 cluster. This is accomplished using isotopomer selective IR-IR hole-burning on the Cs+(D2O)5(H2O) clusters formed by gas-phase exchange of a single, intact H2O molecule for D2O in the Cs+(D2O)6 ion. The OH stretching pattern of the Cs+(H2O)6 isotopologue is accurately recovered by superposition of the isotopomer spectra, thus establishing that the H2O incorporation is random and that the OH stretching manifold is largely due to contributions from decoupled water molecules. This behavior enables a powerful new way to extract structural information from vibrational spectra of size-selected clusters by explicitly identifying the local environments responsible for specific infrared features. The Cs+(H2O)6 structure was unambiguously assigned to the 4.1.1 isomer (a homodromic water tetramer with two additional flanking water molecules) from the fact that its computed IR spectrum matches the observed overall pattern and recovers the embedded correlations in the two OH stretching bands of the water molecule in the Cs+(D2O)5(H2O) isotopomers. The 4.1.1 isomer is the lowest in energy among other candidate networks at advanced (e.g., CCSD(T)) levels of theoretical treatment after corrections for (anharmonic) zero-point energy (ZPE). With the structure in hand, we then explore the mechanical origin of the various band locations using a local electric field formalism. Furthermore, this approach promises to provide a transferrable scheme for the prediction of the OH stretching fundamentals displayed by water networks in close proximity to solute ions.},
doi = {10.1063/1.4941285},
journal = {Journal of Chemical Physics},
number = 7,
volume = 144,
place = {United States},
year = {Wed Feb 17 00:00:00 EST 2016},
month = {Wed Feb 17 00:00:00 EST 2016}
}
Web of Science
Works referenced in this record:
Observation of a Zundel-like transition state during proton transfer in aqueous hydroxide solutions
journal, July 2009
- Roberts, S. T.; Petersen, P. B.; Ramasesha, K.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 36
Understanding the Effects of Hydrogen Bonding at the Vapor−Water Interface: Vibrational Sum Frequency Spectroscopy of H 2 O/HOD/D 2 O Mixtures Studied Using Molecular Dynamics Simulations
journal, June 2007
- Walker, Dave S.; Richmond, Geraldine L.
- The Journal of Physical Chemistry C, Vol. 111, Issue 23
A b i n i t i o relativistic effective potentials with spin–orbit operators. IV. Cs through Rn
journal, November 1990
- Ross, R. B.; Powers, J. M.; Atashroo, T.
- The Journal of Chemical Physics, Vol. 93, Issue 9
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
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
Are water simulation models consistent with steady-state and ultrafast vibrational spectroscopy experiments?
journal, November 2007
- Schmidt, J. R.; Roberts, S. T.; Loparo, J. J.
- Chemical Physics, Vol. 341, Issue 1-3
Measuring Electric Fields and Noncovalent Interactions Using the Vibrational Stark Effect
journal, March 2015
- Fried, Stephen D.; Boxer, Steven G.
- Accounts of Chemical Research, Vol. 48, Issue 4
Vibrational manifestations of strong non-Condon effects in the H3O+·X3 (X = Ar, N2, CH4, H2O) complexes: A possible explanation for the intensity in the “association band” in the vibrational spectrum of water
journal, January 2012
- McCoy, Anne B.; Guasco, Timothy L.; Leavitt, Christopher M.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 20
How the Shape of an H-Bonded Network Controls Proton-Coupled Water Activation in HONO Formation
journal, January 2010
- Relph, R. A.; Guasco, T. L.; Elliott, B. M.
- Science, Vol. 327, Issue 5963
Electric Field Fluctuations Drive Vibrational Dephasing in Water
journal, October 2005
- Eaves, Joel D.; Tokmakoff, Andrei; Geissler, Phillip L.
- The Journal of Physical Chemistry A, Vol. 109, Issue 42
Isolating the spectra of cluster ion isomers using Ar-“tag” -mediated IR-IR double resonance within the vibrational manifolds: Application to NO[sub 2][sup −]⋅H[sub 2]O
journal, January 2008
- Elliott, Ben M.; Relph, Rachael A.; Roscioli, Joseph R.
- The Journal of Chemical Physics, Vol. 129, Issue 9
The structure of gas-phase [Al·nH2O]+: hydrated monovalent aluminium Al+(H2O)n or hydride-hydroxide HAlOH+(H2O)n−1?
journal, January 2011
- Linde, Christian van der; Beyer, Martin K.
- Physical Chemistry Chemical Physics, Vol. 13, Issue 15
Ultrafast Vibrational Energy Transfer between Surface and Bulk Water at the Air-Water Interface
journal, March 2007
- Smits, Marc; Ghosh, Avishek; Sterrer, Martin
- Physical Review Letters, Vol. 98, Issue 9
Hydration of Gaseous Copper Dications Probed by IR Action Spectroscopy
journal, July 2008
- O’Brien, Jeremy T.; Williams, Evan R.
- The Journal of Physical Chemistry A, Vol. 112, Issue 26
Electric Moments of Molecules in Liquids
journal, August 1936
- Onsager, Lars
- Journal of the American Chemical Society, Vol. 58, Issue 8
Combined electronic structure/molecular dynamics approach for ultrafast infrared spectroscopy of dilute HOD in liquid H2O and D2O
journal, May 2004
- Corcelli, S. A.; Lawrence, C. P.; Skinner, J. L.
- The Journal of Chemical Physics, Vol. 120, Issue 17
Vibrational predissociation spectroscopy of Cs + (H 2 O) 1−5
journal, August 1996
- Weinheimer, Corey J.; Lisy, James M.
- The Journal of Chemical Physics, Vol. 105, Issue 7
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989
- Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 90, Issue 2
Development of a low-temperature photoelectron spectroscopy instrument using an electrospray ion source and a cryogenically controlled ion trap
journal, July 2008
- Wang, Xue-Bin; Wang, Lai-Sheng
- Review of Scientific Instruments, Vol. 79, Issue 7
The Effects of Dissolved Halide Anions on Hydrogen Bonding in Liquid Water
journal, November 2007
- Smith, Jared D.; Saykally, Richard J.; Geissler, Phillip L.
- Journal of the American Chemical Society, Vol. 129, Issue 45
Structure of Water at Charged Interfaces: A Molecular Dynamics Study
journal, June 2014
- Dewan, Shalaka; Carnevale, Vincenzo; Bankura, Arindam
- Langmuir, Vol. 30, Issue 27
Proton mobility and stability of water clusters containing alkali metal ions
journal, December 2012
- Zatula, Alexey Sergeevich; Ryding, Mauritz Johan; Andersson, Patrik Urban
- International Journal of Mass Spectrometry, Vol. 330-332
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992
- Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
- The Journal of Chemical Physics, Vol. 96, Issue 9
Optimal geometries and harmonic vibrational frequencies of the global minima of water clusters (H 2 O) n , n = 2–6, and several hexamer local minima at the CCSD(T) level of theory
journal, September 2013
- Miliordos, Evangelos; Aprà, Edoardo; Xantheas, Sotiris S.
- The Journal of Chemical Physics, Vol. 139, Issue 11
Characterization of the potential energy surface of the HO 2 molecular system by a density functional approach
journal, December 1994
- Barone, Vincenzo
- The Journal of Chemical Physics, Vol. 101, Issue 12
Vibrational cooling in a cold ion trap: Vibrationally resolved photoelectron spectroscopy of cold C60− anions
journal, August 2005
- Wang, Xue-Bin; Woo, Hin-Koon; Wang, Lai-Sheng
- The Journal of Chemical Physics, Vol. 123, Issue 5
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010
- Valiev, M.; Bylaska, E. J.; Govind, N.
- Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
Vibrational Stark Spectroscopy. 1. Basic Theory and Application to the CO Stretch
journal, October 1995
- Hush, N. S.; Reimers, J. R.
- The Journal of Physical Chemistry, Vol. 99, Issue 43
Theory of bulk, surface and interface phase transition kinetics in thin films
journal, July 2004
- Backus, Ellen H. G.; Bonn, Mischa
- The Journal of Chemical Physics, Vol. 121, Issue 2
Isotope exchange in reactions between D 2 O and size-selected ionic water clusters containing pyridine, H + (pyridine) m (H 2 O) n
journal, January 2011
- Ryding, Mauritz Johan; Zatula, Alexey S.; Andersson, Patrik Urban
- Phys. Chem. Chem. Phys., Vol. 13, Issue 4
Microhydration of Contact Ion Pairs in M 2+ OH – (H 2 O) n =1–5 (M = Mg, Ca) Clusters: Spectral Manifestations of a Mobile Proton Defect in the First Hydration Shell
journal, June 2014
- Johnson, Christopher J.; Dzugan, Laura C.; Wolk, Arron B.
- The Journal of Physical Chemistry A, Vol. 118, Issue 35
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
A Cluster Study of Anionic Hydration: Spectroscopic Characterization of the I - ·W n , 1 ≤ n ≤ 3, Supramolecular Complexes at the Primary Steps of Solvation
journal, January 1999
- Ayotte, Patrick; Weddle, Gary H.; Kim, Jun
- The Journal of Physical Chemistry A, Vol. 103, Issue 4
Sum frequency generation surface spectra of ice, water, and acid solution investigated by an exciton model
journal, November 2007
- Buch, V.; Tarbuck, T.; Richmond, G. L.
- The Journal of Chemical Physics, Vol. 127, Issue 20
Ultra-broadband sum-frequency spectrometer of aqueous interfaces based on a non-collinear optical parametric amplifier
journal, December 2011
- Isaienko, Oleksandr; Borguet, Eric
- Optics Express, Vol. 20, Issue 1
A b i n i t i o relativistic effective potentials with spin–orbit operators. III. Rb through Xe
journal, September 1987
- LaJohn, L. A.; Christiansen, P. A.; Ross, R. B.
- The Journal of Chemical Physics, Vol. 87, Issue 5
Infrared and Raman Line Shapes of Dilute HOD in Liquid H 2 O and D 2 O from 10 to 90 °C
journal, July 2005
- Corcelli, S. A.; Skinner, J. L.
- The Journal of Physical Chemistry A, Vol. 109, Issue 28
Electrochromism and Solvatochromism
journal, March 1969
- Liptay, W.
- Angewandte Chemie International Edition in English, Vol. 8, Issue 3
Direct catalytic effect and fine modulation of solvent in the keto-enol isomerization of amides
journal, January 1995
- Barone, Vincenzo; Adamo, Carlo; Minichino, Camilla
- Journal of Molecular Structure: THEOCHEM, Vol. 330, Issue 1-3
Efficient Procedure for the Numerical Calculation of Harmonic Vibrational Frequencies Based on Internal Coordinates
journal, March 2013
- Miliordos, Evangelos; Xantheas, Sotiris S.
- The Journal of Physical Chemistry A, Vol. 117, Issue 32
The infrared predissociation spectra of Cl−·H2O·Ar (n=1–5): experimental determination of the influence of Ar solvent atoms
journal, September 2000
- Kelley, J. A.; Weber, J. M.; Lisle, K. M.
- Chemical Physics Letters, Vol. 327, Issue 1-2
Low-lying energy isomers and global minima of aqueous nanoclusters: Structures and spectroscopic features of the pentagonal dodecahedron (H 2 O) 20 and (H 3 O) + (H 2 O) 20
journal, February 2012
- Xantheas, Sotiris S.
- The Canadian Journal of Chemical Engineering, Vol. 90, Issue 4
Charge and Electric Field Fluctuations in Aqueous NaCl Electrolytes
journal, August 2013
- Sellner, Bernhard; Valiev, Marat; Kathmann, Shawn M.
- The Journal of Physical Chemistry B, Vol. 117, Issue 37
Vibrational Characterization of Simple Peptides Using Cryogenic Infrared Photodissociation of H 2 -Tagged, Mass-Selected Ions
journal, April 2011
- Kamrath, Michael Z.; Garand, Etienne; Jordan, Peter A.
- Journal of the American Chemical Society, Vol. 133, Issue 16
Effect of Electric Field on Condensed-Phase Molecular Systems. II. Stark Effect on the Hydroxyl Stretch Vibration of Ice
journal, June 2015
- Shin, Sunghwan; Kang, Hani; Cho, Daeheum
- The Journal of Physical Chemistry C, Vol. 119, Issue 27
Electrochromism, a Possible Change of Color Producible in Dyes by an Electric Field
journal, March 1961
- Platt, John R.
- The Journal of Chemical Physics, Vol. 34, Issue 3
M OLECULAR A SPECTS OF H ALIDE I ON H YDRATION : The Cluster Approach
journal, October 2003
- Robertson, William H.; Johnson, Mark A.
- Annual Review of Physical Chemistry, Vol. 54, Issue 1
IR Spectroscopy and Theory of Cu + (H 2 O)Ar 2 and Cu + (D 2 O)Ar 2 in the O−H (O−D) Stretching Region: Fundamentals and Combination Bands
journal, April 2009
- Carnegie, P. D.; McCoy, A. B.; Duncan, M. A.
- The Journal of Physical Chemistry A, Vol. 113, Issue 17
Persistence of Dual Free Internal Rotation in NH 4 + (H 2 O)·He n =0–3 Ion–Molecule Complexes: Expanding the Case for Quantum Delocalization in He Tagging
journal, April 2015
- Kelleher, Patrick J.; Johnson, Christopher J.; Fournier, Joseph A.
- The Journal of Physical Chemistry A, Vol. 119, Issue 18
Cryogenic Ion Chemistry and Spectroscopy
journal, August 2013
- Wolk, Arron B.; Leavitt, Christopher M.; Garand, Etienne
- Accounts of Chemical Research, Vol. 47, Issue 1
Thermodynamics of Water Dimer Dissociation in the Primary Hydration Shell of the Iodide Ion with Temperature-Dependent Vibrational Predissociation Spectroscopy
journal, February 2015
- Wolke, Conrad T.; Menges, Fabian S.; Tötsch, Niklas
- The Journal of Physical Chemistry A, Vol. 119, Issue 10
Hydration of Alkaline Earth Metal Dications: Effects of Metal Ion Size Determined Using Infrared Action Spectroscopy
journal, September 2009
- Bush, Matthew F.; O’Brien, Jeremy T.; Prell, James S.
- Journal of the American Chemical Society, Vol. 131, Issue 37
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
The statistics of electric field fluctuations in liquid water
journal, February 2009
- Reischl, Bernhard; Köfinger, Jürgen; Dellago, Christoph
- Molecular Physics, Vol. 107, Issue 4-6
Rotational structure in the asymmetric OH stretch of Cs+(H2O)Ar
journal, September 2002
- Vaden, Timothy D.; Forinash, Brian; Lisy, James M.
- The Journal of Chemical Physics, Vol. 117, Issue 10
Insights into Gas-Phase Structural Conformers of Hydrated Rubidium and Cesium Cations, M + (H 2 O) n Ar (M = Rb, Cs; n = 3–5), Using Infrared Photodissociation Spectroscopy
journal, February 2014
- Ke, Haochen; van der Linde, Christian; Lisy, James M.
- The Journal of Physical Chemistry A, Vol. 118, Issue 8
Proton Transfer in Ionic Water Clusters
journal, June 2006
- Sun, Zheng; Siu, Chi-Kit; Balaj, O. Petru
- Angewandte Chemie International Edition, Vol. 45, Issue 24
Structures, energetics, and spectra of aqua-cesium (I) complexes: An ab initio and experimental study
journal, February 2007
- Kołaski, Maciej; Lee, Han Myoung; Choi, Young Cheol
- The Journal of Chemical Physics, Vol. 126, Issue 7
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
Reactions of M + (H 2 O) n , n < 40, M = V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, with D 2 O Reveal Water Activation in Mn + (H 2 O) n
journal, October 2012
- van der Linde, Christian; Beyer, Martin K.
- The Journal of Physical Chemistry A, Vol. 116, Issue 44
Isolating the Spectral Signatures of Individual Sites in Water Networks Using Vibrational Double-Resonance Spectroscopy of Cluster Isotopomers
journal, July 2010
- Guasco, Timothy L.; Elliott, Ben M.; Johnson, Mark A.
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 15
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
A matter of quantum voltages
journal, October 2014
- Sellner, Bernhard; Kathmann, Shawn M.
- The Journal of Chemical Physics, Vol. 141, Issue 18
Computational Investigation of the First Solvation Shell Structure of Interfacial and Bulk Aqueous Chloride and Iodide Ions †
journal, April 2009
- Wick, Collin D.; Xantheas, Sotiris S.
- The Journal of Physical Chemistry B, Vol. 113, Issue 13
Vibrational Spectroscopic Determination of Local Solvent Electric Field, Solute–Solvent Electrostatic Interaction Energy, and Their Fluctuation Amplitudes
journal, December 2011
- Lee, Hochan; Lee, Gayeon; Jeon, Jonggu
- The Journal of Physical Chemistry A, Vol. 116, Issue 1
Works referencing / citing this record:
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
In-depth structural analysis of glycans in the gas phase
journal, January 2019
- Mucha, Eike; Stuckmann, Alexandra; Marianski, Mateusz
- Chemical Science, Vol. 10, Issue 5
Probing the selectivity of Li + and Na + cations on noradrenaline at the molecular level
journal, January 2019
- Ishiuchi, Shun-ichi; Wako, Hiromichi; Xantheas, Sotiris S.
- Faraday Discussions, Vol. 217