Terahertz VRT Spectroscopy of the Water Hexamer-h12 Cage: Dramatic Libration-Induced Enhancement of Hydrogen Bond Tunneling Dynamics

Cole, William T.  S.; Yönder, Özlem; Sheikh, Akber A.; Fellers, Raymond S.; Viant, Mark R.; Saykally, Richard J.; Farrell, James D.; Wales, David J.

doi:10.1021/acs.jpca.8b05777

Title: Terahertz VRT Spectroscopy of the Water Hexamer-h12 Cage: Dramatic Libration-Induced Enhancement of Hydrogen Bond Tunneling Dynamics

Journal Article · Mon Aug 27 00:00:00 EDT 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b05777· OSTI ID:1601190

^[1]; Yönder, Özlem ^[2]; Sheikh, Akber A. ^[1]; Fellers, Raymond S. ^[1]; Viant, Mark R. ^[1];

^[1]; Farrell, James D. ^[3];

^[4]

Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Ruhr-Univ. Bochum, North Rhine-Westphalia, (Germany)
Chinese Academy of Sciences (CAS), Beijing (China). Beijing National Lab. for Condensed Matter Physics, Inst. of Physics
Chinese Academy of Sciences (CAS), Beijing (China). Beijing National Lab. for Condensed Matter Physics, Inst. of Physics; Univ. of Cambridge (United Kingdom)

We report the assignment and analysis of 176 transitions belonging to a librational band of the (H₂O)₆ cage isomer near 525 cm^-1(15 THz). From a fit of the transitions to an asymmetric top model, we observe both dramatic changes in the rotational constants relative to the ground state, indicating significant nonrigidity, and striking enhancement in the tunneling motions that break and reform the hydrogen bonds in the cluster. This is the fifth water cluster system to display such an enhancement in the 15 THz librational region, the details of which may help to elucidate the hydrogen bond dynamics occurring in bulk liquid water.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF); Engineering and Physical Sciences Research Council (EPSRC), United Kingdom

Grant/Contract Number:: AC02-05CH11231; 1300723

OSTI ID:: 1601190

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 122, Issue 37; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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References (47)

Quantum dynamics in the smallest water droplet Clary, D. C. Science, Vol. 351, Issue 6279 https://doi.org/10.1126/science.aaf3061	journal	March 2016
Water clusters: Untangling the mysteries of the liquid, one molecule at a time Keutsch, F. N.; Saykally, R. J. Proceedings of the National Academy of Sciences, Vol. 98, Issue 19 https://doi.org/10.1073/pnas.191266498	journal	September 2001
The water dimer I: Experimental characterization Mukhopadhyay, Anamika; Cole, William T. S.; Saykally, Richard J. Chemical Physics Letters, Vol. 633 https://doi.org/10.1016/j.cplett.2015.04.016	journal	July 2015
The curious case of the water hexamer: Cage vs. Prism Babin, Volodymyr; Paesani, Francesco Chemical Physics Letters, Vol. 580 https://doi.org/10.1016/j.cplett.2013.06.041	journal	August 2013
Getting the Right Answers for the Right Reasons: Toward Predictive Molecular Simulations of Water with Many-Body Potential Energy Functions Paesani, Francesco Accounts of Chemical Research, Vol. 49, Issue 9 https://doi.org/10.1021/acs.accounts.6b00285	journal	August 2016
Structure and torsional dynamics of the water octamer from THz laser spectroscopy near 215 μm Cole, William T. S.; Farrell, James D.; Wales, David J. Science, Vol. 352, Issue 6290 https://doi.org/10.1126/science.aad8625	journal	June 2016
Monitoring Water Clusters “Melt” Through Vibrational Spectroscopy Brown, Sandra E.; Götz, Andreas W.; Cheng, Xiaolu Journal of the American Chemical Society, Vol. 139, Issue 20 https://doi.org/10.1021/jacs.7b03143	journal	May 2017
IR Spectra of the Water Hexamer: Theory, with Inclusion of the Monomer Bend Overtone, and Experiment Are in Agreement Wang, Yimin; Bowman, Joel M. The Journal of Physical Chemistry Letters, Vol. 4, Issue 7 https://doi.org/10.1021/jz400414a	journal	March 2013
Ab initio studies of the conformations of water hexamer: modelling the penta-coordinated hydrogen-bonded pattern in liquid water Kryachko, Eugene S. Chemical Physics Letters, Vol. 314, Issue 3-4 https://doi.org/10.1016/S0009-2614(99)01100-8	journal	December 1999
Energetics and Predissociation Dynamics of Small Water, HCl, and Mixed HCl–Water Clusters Samanta, Amit K.; Wang, Yimin; Mancini, John S. Chemical Reviews, Vol. 116, Issue 9 https://doi.org/10.1021/acs.chemrev.5b00506	journal	February 2016
On the accuracy of density-functional theory exchange-correlation functionals for H bonds in small water clusters. II. The water hexamer and van der Waals interactions Santra, Biswajit; Michaelides, Angelos; Fuchs, Martin The Journal of Chemical Physics, Vol. 129, Issue 19 https://doi.org/10.1063/1.3012573	journal	November 2008
The Role of Anharmonicity in Hydrogen-Bonded Systems: The Case of Water Clusters Temelso, Berhane; Shields, George C. Journal of Chemical Theory and Computation, Vol. 7, Issue 9 https://doi.org/10.1021/ct2003308	journal	August 2011
Hydrogen-bond relaxation dynamics: Resolving mysteries of water ice Huang, Yongli; Zhang, Xi; Ma, Zengsheng Coordination Chemistry Reviews, Vol. 285 https://doi.org/10.1016/j.ccr.2014.10.003	journal	February 2015
Characterization of a cage form of the water hexamer Liu, K.; Brown, M. G.; Carter, C. Nature, Vol. 381, Issue 6582 https://doi.org/10.1038/381501a0	journal	June 1996
Many-Body Interactions in Ice Pham, C. Huy; Reddy, Sandeep K.; Chen, Karl Journal of Chemical Theory and Computation, Vol. 13, Issue 4 https://doi.org/10.1021/acs.jctc.6b01248	journal	March 2017
Pinning Down the Water Hexamer Saykally, R. J.; Wales, D. J. Science, Vol. 336, Issue 6083 https://doi.org/10.1126/science.1222007	journal	May 2012
Water hexamer clusters: Structures, energies, and predicted mid-infrared spectra Losada, Martin; Leutwyler, Samuel The Journal of Chemical Physics, Vol. 117, Issue 5 https://doi.org/10.1063/1.1487371	journal	August 2002
Hydrogen Bonding and OH-Stretch Spectroscopy in Water: Hexamer (Cage), Liquid Surface, Liquid, and Ice Tainter, C. J.; Ni, Y.; Shi, L. The Journal of Physical Chemistry Letters, Vol. 4, Issue 1 https://doi.org/10.1021/jz301780k	journal	December 2012
The water hexamer: Three-body interactions, structures, energetics, and OH-stretch spectroscopy at finite temperature Tainter, C. J.; Skinner, J. L. The Journal of Chemical Physics, Vol. 137, Issue 10 https://doi.org/10.1063/1.4746157	journal	September 2012
Terahertz Laser Vibration−Rotation Tunneling Spectroscopy and Dipole Moment of a Cage Form of the Water Hexamer Liu, K.; Brown, M. G.; Saykally, R. J. The Journal of Physical Chemistry A, Vol. 101, Issue 48 https://doi.org/10.1021/jp9707807	journal	November 1997
Structures of Cage, Prism, and Book Isomers of Water Hexamer from Broadband Rotational Spectroscopy Perez, C.; Muckle, M. T.; Zaleski, D. P. Science, Vol. 336, Issue 6083 https://doi.org/10.1126/science.1220574	journal	May 2012
Concerted hydrogen-bond breaking by quantum tunneling in the water hexamer prism Richardson, J. O.; Perez, C.; Lobsiger, S. Science, Vol. 351, Issue 6279 https://doi.org/10.1126/science.aae0012	journal	March 2016
The Water Dipole Moment in Water Clusters Gregory, J. K. Science, Vol. 275, Issue 5301 https://doi.org/10.1126/science.275.5301.814	journal	February 1997
The Water Hexamer: Cage, Prism, or Both. Full Dimensional Quantum Simulations Say Both Wang, Yimin; Babin, Volodymyr; Bowman, Joel M. Journal of the American Chemical Society, Vol. 134, Issue 27 https://doi.org/10.1021/ja304528m	journal	June 2012
CCSD(T) Complete Basis Set Limit Relative Energies for Low-Lying Water Hexamer Structures Bates, Desiree M.; Tschumper, Gregory S. The Journal of Physical Chemistry A, Vol. 113, Issue 15 https://doi.org/10.1021/jp8105919	journal	April 2009
Analytic MP2 frequencies without fifth-order storage. Theory and application to bifurcated hydrogen bonds in the water hexamer Head-Gordon, Martin; Head-Gordon, Teresa Chemical Physics Letters, Vol. 220, Issue 1-2 https://doi.org/10.1016/0009-2614(94)00116-2	journal	March 1994
Structures, binding energies, and spectra of isoenergetic water hexamer clusters: Extensive ab initio studies Kim, Jongseob; Kim, Kwang S. The Journal of Chemical Physics, Vol. 109, Issue 14 https://doi.org/10.1063/1.477211	journal	October 1998
Low-Energy Structures and Vibrational Frequencies of the Water Hexamer: Comparison with Benzene-(H2O)6 Kim, Kyungsun; Jordan, Kenneth D.; Zwier, Timothy S. Journal of the American Chemical Society, Vol. 116, Issue 25 https://doi.org/10.1021/ja00104a047	journal	December 1994
Theoretical Study of the Cage Water Hexamer Structure Gregory, Jonathon K.; Clary, David C. The Journal of Physical Chemistry A, Vol. 101, Issue 36 https://doi.org/10.1021/jp9703871	journal	September 1997
Structures of the water hexamer using density functional methods Lee, Chengteh; Chen, Han; Fitzgerald, George The Journal of Chemical Physics, Vol. 101, Issue 5 https://doi.org/10.1063/1.467434	journal	September 1994
Intermolecular Interaction in Water Hexamer Chen, Yiming; Li, Hui The Journal of Physical Chemistry A, Vol. 114, Issue 43 https://doi.org/10.1021/jp104822e	journal	November 2010
The monocyclic water hexamer detected in neon matrices by infrared spectroscopy Hirabayashi, Shinichi; Yamada, Koichi M. T. Chemical Physics Letters, Vol. 435, Issue 1-3 https://doi.org/10.1016/j.cplett.2006.12.083	journal	February 2007
Formation of Cyclic Water Hexamer in Liquid Helium: The Smallest Piece of Ice Nauta, K. Science, Vol. 287, Issue 5451 https://doi.org/10.1126/science.287.5451.293	journal	January 2000
Hydrogen Bond Cooperativity and the Three-Dimensional Structures of Water Nonamers and Decamers Pérez, Cristóbal; Zaleski, Daniel P.; Seifert, Nathan A. Angewandte Chemie International Edition, Vol. 53, Issue 52 https://doi.org/10.1002/anie.201407447	journal	October 2014
Hydrogen bond breaking dynamics in the water pentamer: Terahertz VRT spectroscopy of a 20 μ m libration Cole, William T. S.; Fellers, Raymond S.; Viant, Mark R. The Journal of Chemical Physics, Vol. 146, Issue 1 https://doi.org/10.1063/1.4973418	journal	January 2017
Far-infrared VRT spectroscopy of the water dimer: Characterization of the 20 μ m out-of-plane librational vibration Cole, William T. S.; Fellers, Ray S.; Viant, Mark R. The Journal of Chemical Physics, Vol. 143, Issue 15 https://doi.org/10.1063/1.4933116	journal	October 2015
Far-infrared laser vibration–rotation–tunneling spectroscopy of water clusters in the librational band region of liquid water Keutsch, Frank N.; Fellers, Ray S.; Viant, Mark R. The Journal of Chemical Physics, Vol. 114, Issue 9 https://doi.org/10.1063/1.1337052	journal	March 2001
Terahertz VRT spectroscopy of the water hexamer-d ₁₂ prism: Dramatic enhancement of bifurcation tunneling upon librational excitation Cole, William T. S.; Farrell, James D.; Sheikh, Akber A. The Journal of Chemical Physics, Vol. 148, Issue 9 https://doi.org/10.1063/1.5006195	journal	March 2018
Tunable far infrared laser spectrometers Blake, G. A.; Laughlin, K. B.; Cohen, R. C. Review of Scientific Instruments, Vol. 62, Issue 7 https://doi.org/10.1063/1.1142409	journal	July 1991
The Berkeley tunable far infrared laser spectrometers Blake, G. A.; Laughlin, K. B.; Cohen, R. C. Review of Scientific Instruments, Vol. 62, Issue 7 https://doi.org/10.1063/1.1142410	journal	July 1991
A long path length pulsed slit valve appropriate for high temperature operation: Infrared spectroscopy of jet‐cooled large water clusters and nucleotide bases Liu, Kun; Fellers, Raymond S.; Viant, Mark R. Review of Scientific Instruments, Vol. 67, Issue 2 https://doi.org/10.1063/1.1146605	journal	February 1996
PGOPHER: A program for simulating rotational, vibrational and electronic spectra Western, Colin M. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 186 https://doi.org/10.1016/j.jqsrt.2016.04.010	journal	January 2017
Anharmonic vibrational properties by a fully automated second-order perturbative approach Barone, Vincenzo The Journal of Chemical Physics, Vol. 122, Issue 1 https://doi.org/10.1063/1.1824881	journal	January 2005
Vibrational zero-point energies and thermodynamic functions beyond the harmonic approximation Barone, Vincenzo The Journal of Chemical Physics, Vol. 120, Issue 7 https://doi.org/10.1063/1.1637580	journal	February 2004
Hydrogen bond network rearrangement dynamics in water clusters: Effects of intermolecular vibrational excitation on tunneling rates Cole, William T. S.; Saykally, Richard J. The Journal of Chemical Physics, Vol. 147, Issue 6 https://doi.org/10.1063/1.4997046	journal	August 2017
Hydrogen-bond kinetics in liquid water Luzar, Alenka; Chandler, David Nature, Vol. 379, Issue 6560 https://doi.org/10.1038/379055a0	journal	January 1996
Nuclear Quantum Effects in Water Reorientation and Hydrogen-Bond Dynamics Wilkins, David M.; Manolopoulos, David E.; Pipolo, Silvio The Journal of Physical Chemistry Letters, Vol. 8, Issue 12 https://doi.org/10.1021/acs.jpclett.7b00979	journal	May 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Water cluster
hydrogen bond
tunneling
libration

Title: Terahertz VRT Spectroscopy of the Water Hexamer-h12 Cage: Dramatic Libration-Induced Enhancement of Hydrogen Bond Tunneling Dynamics

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