Neutron-diffraction investigation of the intramolecular structure of a water molecule in the liquid phase at high temperatures

Ichikawa, Kazuhiko; Kameda, Yasuo; Yamaguchi, Toshio; Wakita, Hisanobu; Misawa, Masakatsu

doi:10.1080/00268979100101071

Cited by 155 publications

(116 citation statements)

References 20 publications

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“…5), with average values expanded by ∼0.4 • and ∼0.01 Å relative to the monomer. This trend is consistent with experimental results, 42 but is not captured by most flexible models. 14,15 Geometry-dependent electronic polarization has been suggested as a requirement for capturing this effect correctly.…”

Section: B Polarization and Dielectric Responsesupporting

confidence: 81%

“…Reorganization of electron pairs also contributes, resulting in accurate dipolar and quadrupolar changes. In this respect, LEWIS addresses a longstanding problem of simple flexible and polarizable empirical water models that have difficulties in reproducing the experimentally observed 42 and quantum mechanically supported 43 changes of the water geometry in the liquid state. 11,14,44,45 …”

Section: Introductionmentioning

confidence: 99%

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Natural polarizability and flexibility via explicit valency: The case of water

Kale

Herzfeld

2012

The Journal of Chemical Physics

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As the dominant physiological solvent, water drives the folding of biological macromolecules, influences conformational changes, determines the ionization states of surface groups, actively participates in catalytic events, and provides "wires" for long-range proton transfer. Elucidation of all these roles calls for atomistic simulations. However, currently available methods do not lend themselves to efficient simulation of proton transfer events, or even polarizability and flexibility. Here, we report that an explicit account of valency can provide a unified description for the polarizability, flexibility, and dissociability of water in one intuitive and efficient setting. We call this approach LEWIS, after the chemical theory that inspires the use of valence electron pairs. In this paper, we provide details of the method, the choice of the training set, and predictions for the neat ambient liquid, with emphasis on structure, dynamics, and polarization. LEWIS water provides a good description of bulk properties, and dipolar and quadrupolar responses.

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Section: B Polarization and Dielectric Responsesupporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Natural polarizability and flexibility via explicit valency: The case of water

Kale

Herzfeld

2012

The Journal of Chemical Physics

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“…To our knowledge, intramolecular structure parameters for a 2-propanol molecule determined by X-ray and neutron diffraction methods are not available in the literature and thus were estimated from those of an ethanol molecule previously determined from neutron diffraction measurements [25]. The structure parameters of a 2-propanol molecule employed in the present analysis are summarized in Table 1, together with those of water molecules [26]. The peaks beyond 2.8Å arise mainly from intermolecular interactions among 2-propanol molecules.…”

Section: X-ray Data Treatmentmentioning

confidence: 99%

“…1) to evaluate the long-range interactions of 2-propanol-2-propanol, 2-propanol-water, and water-water in the so- lutions and confirm the number of hydrogen bonds estimated from the peak separation procedure in the r-space as described in the previous section. In the present analysis the structure parameters of the intramolecular interactions 2-propanol and water [26] molecules as listed in Table 1 were fixed during the analysis. For pure 2-propanol, as discussed in the previous section, the total RDF in the r-range from 2 to 7Å can be explained by the structure model of the cis-formed 2-propanol chain.…”

Section: Least-squares Refinements For Structure Functionsmentioning

confidence: 99%

Large-Angle X-ray Scattering Investigation of the Structure of 2-Propanol–Water Mixtures

Takamuku

Saisho

Aoki

et al. 2002

Zeitschrift Für Naturforschung A

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The structure of 2-propanol and its aqueous mixtures has been investigated at 25 C, using a large-angle X-ray scattering (LAXS) technique. The total radial distribution function of neat 2-propanol has shown that hydrogen-bonded chains of 2-propanol molecules are formed. In the 2-propanol-water mixtures, 2-propanol chains predominate at mole fractions x 2pr > 0.1. When x 2pr decreases from x 2pr = 1, the number of hydrogen bonds reaches a plateau of 3.4 0.1 at x 2pr 0.1, suggesting that the tetrahedral-like structure of water is mainly formed. On the basis of the present findings, together with previous results on methanol-water and ethanol-water mixtures, effects of hydrophobic groups on the structure of the alcohol-water mixtures are discussed. The heat of mixing at 25 C as a function of x 2pr has been interpreted in terms of the structural transition of solvent clusters.

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“…143 However, the water geometry was severely distorted from the gas-phase structure and the average bond lengths and angles in the liquid states are both significantly larger than commonly accepted values of liquid water. 143,144 The results displayed in Figure 9 show that the change in electronic polarization at different thermodynamic state points also makes critical contributions to the variation of the molecular dipole moment.…”

Section: Ivb2 Temperature-dependent Liquid Propertiesmentioning

confidence: 97%

Quantum mechanical force field for water with explicit electronic polarization

Han

Mazack

Zhang

et al. 2013

The Journal of Chemical Physics

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A quantum mechanical force field (QMFF) for water is described. Unlike traditional approaches that use quantum mechanical results and experimental data to parameterize empirical potential energy functions, the present QMFF uses a quantum mechanical framework to represent intramolecular and intermolecular interactions in an entire condensed-phase system. In particular, the internal energy terms used in molecular mechanics are replaced by a quantum mechanical formalism that naturally includes electronic polarization due to intermolecular interactions and its effects on the force constants of the intramolecular force field. As a quantum mechanical force field, both intermolecular interactions and the Hamiltonian describing the individual molecular fragments can be parameterized to strive for accuracy and computational efficiency. In this work, we introduce a polarizable molecular orbital model Hamiltonian for water and for oxygen-and hydrogen-containing compounds, whereas the electrostatic potential responsible for intermolecular interactions in the liquid and in solution is modeled by a three-point charge representation that realistically reproduces the total molecular dipole moment and the local hybridization contributions. The present QMFF for water, which is called the XP3P (explicit polarization with three-point-charge potential) model, is suitable for modeling both gas-phase clusters and liquid water. The paper demonstrates the performance of the XP3P model for water and proton clusters and the properties of the pure liquid from about 900 × 10 6 self-consistent-field calculations on a periodic system consisting of 267 water molecules. The unusual dipole derivative behavior of water, which is incorrectly modeled in molecular mechanics, is naturally reproduced as a result of an electronic structural treatment of chemical bonding by XP3P. We anticipate that the XP3P model will be useful for studying proton transport in solution and solid phases as well as across biological ion channels through membranes. © 2013 AIP Publishing LLC.

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Neutron-diffraction investigation of the intramolecular structure of a water molecule in the liquid phase at high temperatures

Cited by 155 publications

References 20 publications

Natural polarizability and flexibility via explicit valency: The case of water

Natural polarizability and flexibility via explicit valency: The case of water

Large-Angle X-ray Scattering Investigation of the Structure of 2-Propanol–Water Mixtures

Quantum mechanical force field for water with explicit electronic polarization

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