Water Clusters

Liu, Kristina; Cruzan, J. D.; Saykally, Richard J.

doi:10.1126/science.271.5251.929

Cited by 740 publications

(581 citation statements)

References 63 publications

(10 reference statements)

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“…Due to the large difference in the librational moments of inertia, separation of the six intermolecular degrees of freedom into distinct donor/acceptor vibrational modes should be a much better approximation for water-methanol than for the water dimer, for which recent high resolution far-infrared spectra 50 have revealed breakdowns in the high barrier generalized internal axis method so successfully used for the ground state of (H 2 O) 2 . 1, 21,22 In this limit, the out-of-plane and in-plane bends of the donor water should be the stiffest, highest-frequency modes.…”

Section: Discussionmentioning

confidence: 99%

Microwave rotation-tunneling spectroscopy of the water–methanol dimer: Direct structural proof for the strongest bound conformation

Stockman

Blake

Lovas

et al. 1997

The Journal of Chemical Physics

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O between 7 and 24 GHz using a Fourier-transform microwave spectrometer. Because CH 3 OH and H 2 O are capable of both accepting and donating hydrogen bonds, there exists some question as to which donor-acceptor pairing of the molecules is the lowest energy form. This question is further emphasized by the ambiguity and variety present in previous experimental and computational results. Transitions arising from the methyl torsional A state were assigned in each of the studied isotopomers, and for the A and E states in , where the errors correspond to 1 uncertainties-are consistent with either conformation, the fit of the structure to the rotational constants demonstrates unambiguously that the lower-energy conformation formed in supersonically cooled molecular beams corresponds to a water-donor, methanol-acceptor complex. The results and implications for future work are also discussed in terms of the permutation-inversion theory presented by Hougen and Ohashi ͓J. Mol. Spectros. 159, 363 ͑1993͔͒.

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Section: Discussionmentioning

confidence: 99%

Microwave rotation-tunneling spectroscopy of the water–methanol dimer: Direct structural proof for the strongest bound conformation

Stockman

Blake

Lovas

et al. 1997

The Journal of Chemical Physics

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“…Despite numerous experimental and theoretical studies [64][65][66][67][68][69][70][71] , the physical nature of hydrogen bonding is still under debate. One issue is the degree of covalency in the hydrogen bonding, which is determined by the extent of intermolecular electron delocalization or CT [70][71][72][73][74] .…”

Section: Physical Nature Of Hydrogen Bonding In the Water Dimermentioning

confidence: 99%

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Khaliullin

Kühne

2013

Phys. Chem. Chem. Phys.

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The application of newly developed first-principle modeling techniques to liquid water deepens our understanding of the microscopic origins of its unusual macroscopic properties and behaviour. Here, we review two novel ab initio computational methods: second-generation Car-Parrinello molecular dynamics and decomposition analysis based on absolutely localized molecular orbitals. We show that these two methods in combination not only enable ab initio molecular dynamics simulations on previously inaccessible time and length scales, but also provide unprecedented insights into the nature of hydrogen bonding between water molecules. We discuss recent applications of these methods to water clusters and bulk water. CONTENTS

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“…For the dissociation of H ϩ ͑CH 3 OH͒ 4 H 2 O, the two most likely forms of the products emerging from the methanol loss channels are whereas it is for the water loss. They are, respectively, the lowest-energy isomers of H ϩ ͑CH 3 This work, we believe, presents the first experimental identification of cluster isomers from their fragmentdependent vibrational predissociation spectra. Using the mixed methanol-water cluster ion H ϩ ͑CH 3 OH͒ 4 H 2 O as a test system, it is demonstrated herein that vibrational predissociation spectroscopy in combination with mass-selected detection of photofragments allows for a clearer identification of cluster isomers than the temperature-dependence measurements previously presented.…”

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confidence: 99%

“…This is particularly the case for neutral clusters whose sizes are difficult to determine unambiguously. Although there have been several successful examples in this direction, [3][4][5] the range of exploration is expected to be severely limited by the lack of proper mass-selection means. For charged clusters, this limitation is apparently removed since they can be easily sizeselected by mass spectrometry.…”

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confidence: 99%

Identification of CH3OH2+ and H3O+-centered cluster isomers from fragment-dependent vibrational predissociation spectra of H+(CH3OH)4H2O

Chaudhuri

Jiang

Wang

et al. 2000

The Journal of Chemical Physics

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Cluster isomers of H ϩ ͑CH 3 OH͒ 4 H 2 O have been identified by vibrational predissociation spectroscopy in combination with mass-selected detection of photofragments. Ab initio calculations indicate that the cluster ion can exist in either CH 3 OH 2 ϩ ͑CH 3 OH͒ 3 H 2 O or H 3 O ϩ ͑CH 3 OH͒ 4 isomeric forms. They can dissociate via a methanol loss or water loss channel, depending on the structure of the isomers. While water loss is the dominant channel of the dissociation, the methanol loss channel is readily accessible by the H 3 O ϩ -centered cluster isomer. We demonstrate in this study that mass-selected detection of photofragments produced by vibrational excitation is an effective way of identifying cluster isomers in the gas phase. © 2000 American Institute of Physics. ͓S0021-9606͑00͒01917-6͔A central issue in the studies of atomic and molecular clusters has been the identification of structural isomers. Studies on this subject have been extensive in the past three decades, 1 leading to the discovery and suggestion of many interesting macromolecular structures. One noticeable example is the identification of the structure of carbon clusters by ion mobility measurements using a drift tube. Monocyclic as well as polycyclic rings have been suggested to be stable isomers of the C 60 ϩ cluster ion, 2 in addition to the spheroidal fullerenes. Unfortunately, up to now, detailed spectroscopic examination of these intriguing cluster isomers remains lacking. Identification of cluster isomers by spectroscopic means has been deemed a difficult task. This is particularly the case for neutral clusters whose sizes are difficult to determine unambiguously. Although there have been several successful examples in this direction, 3-5 the range of exploration is expected to be severely limited by the lack of proper mass-selection means. For charged clusters, this limitation is apparently removed since they can be easily sizeselected by mass spectrometry. We have recently reported on the observations of various cluster isomers of NH 4 ϩ ͑H 2 O͒ 2-7 , 6 H ϩ ͑CH 3 OH͒ 4,5 , 7 H ϩ ͓͑CH 3 ͒ 2 O͔͒ 2 ͑H 2 O͒, 8 and H ϩ ͑CH 3 OH͒͑H 2 O͒ 1-6 ͑Ref. 9͒ using vibrational predissociation spectroscopy. Identification of the isomers was accomplished by varying cluster temperature over a range of Ϯ20 K and observing the corresponding peak intensity changes with the temperature. Here, we report a new and alternative means of identifying cluster isomers and demonstrate the feasibility of this approach, which involves mass-selected detection of photofragments, using the mixed methanolwater cluster ions H ϩ ͑CH 3 OH͒ 4 H 2 O as a benchmark system. A mixed methanol-water cluster ion ͓H ϩ ͑CH 3 OH͒ m (H 2 O) n ͔ can exist in a variety of isomeric forms. Interestingly, they can be either centered with CH 3 OH 2 ϩ or with H 3 O ϩ , depending on the structure and size of the cluster. Previous experiments 9-12 and calculations 9 have shown that these two isomeric forms ͑CH 3 OH 2 ϩ and H 3 O ϩ -centered͒ are comparable in stability when the cluster is...

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Water Clusters

Cited by 740 publications

References 63 publications

Microwave rotation-tunneling spectroscopy of the water–methanol dimer: Direct structural proof for the strongest bound conformation

Microwave rotation-tunneling spectroscopy of the water–methanol dimer: Direct structural proof for the strongest bound conformation

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Identification of CH3OH2+ and H3O+-centered cluster isomers from fragment-dependent vibrational predissociation spectra of H+(CH3OH)4H2O

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