Systematic Study of the Spectroscopic Properties of Isotopically Substituted Water by MD Simulations

Lu, Tinghai; Tóth, Gergely; Heinzinger, K.

doi:10.1021/jp951546o

Cited by 7 publications

(3 citation statements)

References 22 publications

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“…Figure shows the three angular velocity autocorrelation functions and the corresponding rotational spectral densities. The calculation of the rotational spectral densities is based on the treatment of Heinzinger et al on the spectroscopic properties of substituted water . Librations around the x and y axes (in the principal axis coordinate system) are quasidegenerate with maxima located at 200 cm -1 , while the peak of the in-plane libration (around the z axis) shifts toward lower wavenumbers (approximately 100 cm -1 ).…”

Section: Resultsmentioning

confidence: 99%

A Comprehensive Liquid Simulation Study of Neat Formic Acid

et al. 2000

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An extensive liquid simulation study combining Monte Carlo and molecular dynamics techniques was performed for liquid formic acid. We investigated thermodynamic, dynamic, and spectroscopic properties of the liquid. The examination of several dynamic properties leads to a detailed picture of the molecular contributions to the macroscopic properties of the liquid phase. Although the present model overestimates the diffusion constant by about 25%, the calculated spectral densities for the translational and rotational modes of the solvent in combination with ab initio calculated harmonic frequencies provide a valuable tool in the qualitative assignment of several important features of the low-frequency liquid phase Raman spectrum. The relaxation time scales also give reasonably good agreement with dielectric relaxation and NMR measurements. Hydrogen-bonding dynamics provide interesting additional information on the dynamical time scales. The average lifetime of the strongest types of hydrogen bonds is less than 0.5 ps. The relative population of the dimers with two hydrogen bonds undergoes a significant change relative to the gas phase population, the weight of the less stable dimers increasing substantially. Approximately 1% of the molecules participate in hydrogen-bonding patterns which dominate the crystalline phase of the formic acid. As an extension of the present work for the liquid phase, we have also performed calculations for the vapor-liquid equilibrium coexistence curve predicting the critical temperature with 5% error. The application of the thermodynamic integration method results in thermodynamic excess quantities as the excess free energy, entropy, and chemical potential.

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Section: Resultsmentioning

confidence: 99%

A Comprehensive Liquid Simulation Study of Neat Formic Acid

et al. 2000

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“…The spectroscopic properties of isotopically substituted BJH water have also been studied (Lu et al 1996).…”

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confidence: 99%

Molecular Simulations of Liquid and Supercritical Water: Thermodynamics, Structure, and Hydrogen Bonding

Kalinichev¹

2001

Reviews in Mineralogy and Geochemistry

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“…Water molecules are, beyond a doubt, flexible in nature. Furthermore, it is known that the isotopic substitutions noticeably affect the vibrational properties of water 13 and also that there is a degree of coupling between intermolecular and intramolecular modes. Since intramolecular vibrations are generally high frequency oscillations a quantum rather a classical description of these vibration would be desirable 14 .…”

Section: Introductionmentioning

confidence: 99%

A study of the influence of isotopic substitution on the melting point and temperature of maximum density of water by means of path integral simulations of rigid models

McBride

Aragonés

Noya

et al. 2012

Phys. Chem. Chem. Phys.

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The melting point of ice I(h), as well as the temperature of maximum density (TMD) in the liquid phase, has been computed using the path integral Monte Carlo method. Two new models are introduced, TIP4PQ_D2O and TIP4PQ_T2O, which are specifically designed to study D(2)O and T(2)O respectively. We have also used these models to study the "competing quantum effects" proposal of Habershon, Markland and Manolopoulos; the TIP4PQ/2005, TIP4PQ/2005 (D(2)O) and TIP4PQ/2005 (T(2)O) models are able to study the isotopic substitution of hydrogen for deuterium or tritium whilst constraining the geometry, while the TIP4PQ_D2O and TIP4PQ_T2O models, where the O-H bond lengths are progressively shortened, permit the study of the influence of geometry (and thus dipole moment) on the isotopic effects. For TIP4PQ_D2O-TIP4PQ/2005 we found a melting point shift of 4.9 K (experimentally the value is 3.68 K) and a TMD shift of 6 K (experimentally 7.2 K). For TIP4PQ_T2O-TIP4PQ/2005 we found a melting point shift of 5.2 K (experimentally the value is 4.49 K) and a TMD shift of 7 K (experimentally 9.4 K).

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Systematic Study of the Spectroscopic Properties of Isotopically Substituted Water by MD Simulations

Cited by 7 publications

References 22 publications

A Comprehensive Liquid Simulation Study of Neat Formic Acid

A Comprehensive Liquid Simulation Study of Neat Formic Acid

Molecular Simulations of Liquid and Supercritical Water: Thermodynamics, Structure, and Hydrogen Bonding

A study of the influence of isotopic substitution on the melting point and temperature of maximum density of water by means of path integral simulations of rigid models

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