Dimers of the Water Molecule in the Earth's Atmosphere

Gebbie, H. A.; Burroughs, William James; Chamberlain, J.; Harries, J. E.; Jones, R. G.

doi:10.1038/221143a0

Cited by 126 publications

(54 citation statements)

References 13 publications

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“…Exp ) 0.00(0.75) / 0.00(0.79) (2) (1) and (2) with quantum numbers K = 0 and K = 1, respectively, as defined in Eq. (39); the values in parentheses are the interchange tunneling splittings i 1 (K) and i 2 (K), also defined in the text.…”

Section: K=0 K=1mentioning

confidence: 99%

“…In order to add flexibility to the recent very accurate CCpol-8s potential, we used the following simple prescription to define the pair potential V (2) CCpol-8sf :…”

Section: A Flexible Ccpol-8s Potentialmentioning

confidence: 99%

“…1 This is due to both the importance of the isolated dimer, in particular for atmospheric science, 2,3 and to the fact that the dimer interactions constitute the leading and most important term in a many-body expansion for water clusters and condensed phases of water. 1,4 The main source of experimental information on water dimer comes from spectral measurements.…”

Section: Introductionmentioning

confidence: 99%

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Spectra of water dimer from a new ab initio potential with flexible monomers

Leforestier

Szalewicz

Avoird

2012

The Journal of Chemical Physics

111

164

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Communication: Determination of the bond dissociation energy (D0) of the water dimer, (H2O)2, by velocity map imaging The Journal of Chemical Physics 134, 211101211101 (2011) We report the definition and testing of a new ab initio 12-dimensional potential for the water dimer with flexible monomers. Using our recent accurate CCpol-8s rigid water pair potential [W. Cencek, K. Szalewicz, C. Leforestier, R. van Harrevelt, and A. van der Avoird, Phys. Chem. Chem. Phys. 10, 4716 (2008)] as a reference for the undistorted monomers' geometries, a distortion correction has been added, which was taken from a former flexible-monomer ab initio potential. This correction allows us to retrieve the correct binding energy D e = 21.0 kJ mol −1 , and leads to an equilibrium geometry in close agreement with the one obtained from benchmark calculations. The kinetic energy operator describing the flexible-monomer water dimer has been expressed in terms of Radau coordinates for each monomer and a recent general cluster polyspherical formulation describing their relative motions. Within this formulation, an adiabatic scheme has been invoked in order to decouple fast (intramolecular) modes and slow (intermolecular) ones. Different levels of approximation were tested, which differ in the way in which the residual potential coupling between the intramolecular modes located on different monomers and the dependence of the monomer rotational constants on the dimer geometry are handled. Accurate calculations of the vibration-rotation-tunneling levels of (H 2 O) 2 and (D 2 O) 2 were performed, which show the best agreement with experiments achieved so far for any water potential. Intramolecular excitations of the two monomers were calculated within two limiting cases, to account for the lack of non-adiabatic coupling between intramolecular modes due to the intermolecular motion. In the first model, the excitation was assumed to stay either on the donor or the acceptor molecule, and to hop between the two moieties upon donor-acceptor interchange. In the second model, the excitation remains on the same molecule whatever is the dimer geometry. Marginal frequency differences, less than 2 cm −1 , were obtained for all modes, and the resulting infrared shifts are in good agreement with experiments.

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Section: K=0 K=1mentioning

confidence: 99%

“…In order to add flexibility to the recent very accurate CCpol-8s potential, we used the following simple prescription to define the pair potential V (2) CCpol-8sf :…”

Section: A Flexible Ccpol-8s Potentialmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Spectra of water dimer from a new ab initio potential with flexible monomers

Leforestier

Szalewicz

Avoird

2012

The Journal of Chemical Physics

111

164

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“…Their homogenous gas phase reaction produces some oxidant, complexes and stable molecules in the atmosphere, so its reaction will be important. [25][26][27] In this work, the role of relative humidity are reviewed by the effect of water and water dimer molecule in the structural, energy profile of mercury oxidation by ozone. For evaluating of results of water and water dimer molecule reaction with ozone-mercury complex, in the first step, ozone-mercury complex (IMr1) reacts with water and water dimer and produce two reactant complexes IMr2, and IMr3, respectively.…”

Section: Mercury-ozone Reaction With Water and Water Dimer Moleculesmentioning

confidence: 99%

Mechanistic Study on the Ozone‐Mercury Reaction and the Effect of Water and Water Dimer Molecules

Vahedpour

Tozihi

Nazari

2011

J Chinese Chemical Soc

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The thermodynamics and mechanism of the reaction of elemental mercury with ozone has been studied computationally. The effect of water and water dimer molecules on the reaction has also been investigated. For dry reaction, we obtained two pathways and geometry optimization, atoms in molecules analysis and vibrational frequencies of all component of reaction have been used for confirming of reaction mechanism. Thermodynamic variable of reaction has been calculated. For the reaction in the presence of the water, our studies focus on ozone-mercury complex reaction with water and water dimer and obtained the mechanism of reactions. Comparison of wet and dry reaction shows the energy profile of reaction decreases with water molecule correspond to experimental prediction. Calculated thermodynamic variable of all reaction shows the Gibbs free energy of reaction decreases with the number of water molecule.

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“…The difference in the description is readily apparent: the QM curve is shifted to a weaker interaction and to a longer distance at the minimum, with respect to the MM curve. Reported experimental values, of 2.98Å for the oxygen-oxygen separation [32,33], and ranging from 3.6 to 5.2 kcal/mol for the magnitude of the interaction at the minimum energy geometry [34][35][36][37], are better reproduced by the quantum-mechanical model, which provides an optimized hydrogen-bond energy of 4.9 kcal/mol at 2.9Å. Similar results have been obtained from previous DFT calculations based on both localized and extended basis functions [38][39][40][41][42].…”

Section: Assessment Of the Model: Water Dimer And Aqueous Liquid Phasementioning

confidence: 99%

A quantum-mechanics molecular-mechanics scheme for extended systems

Hunt¹,

Sánchez²,

Scherlis³

2016

J. Phys.: Condens. Matter

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We introduce and discuss a hybrid quantum-mechanics molecular-mechanics (QM-MM) approach for Car-Parrinello DFT simulations with pseudopotentials and planewaves basis, designed for the treatment of periodic systems. In this implementation the MM atoms are considered as additional QM ions having fractional charges of either sign, which provides conceptual and computational simplicity by exploiting the machinery already existing in planewave codes to deal with electrostatics in periodic boundary conditions.With this strategy, both the QM and MM regions are contained in the same supercell, which determines the periodicity for the whole system. Thus, while this method is not meant to compete with non-periodic QM-MM schemes able to handle extremely large but finite MM regions, it is shown that for periodic systems of a few hundred atoms, our approach provides substantial savings in computational times by treating classically a fraction of the particles. The performance and accuracy of the method is assessed through the study of energetic, structural, and dynamical aspects of the water dimer and of the aqueous bulk phase. Finally, the QM-MM scheme is applied to the computation of the vibrational spectra of water layers adsorbed at the TiO 2 anatase (101) solid-liquid interface. This investigation suggests that the inclusion of a second monolayer of H 2 O molecules is sufficient to induce on the first adsorbed layer, a vibrational dynamics similar to that taking place in the presence of an aqueous environment. The present QM-MM scheme appears as a very interesting tool to efficiently perform molecular dynamics simulations of complex condensed matter systems, from solutions to nanoconfined fluids to different kind of interfaces.

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Dimers of the Water Molecule in the Earth's Atmosphere

Cited by 126 publications

References 13 publications

Spectra of water dimer from a new ab initio potential with flexible monomers

Spectra of water dimer from a new ab initio potential with flexible monomers

Mechanistic Study on the Ozone‐Mercury Reaction and the Effect of Water and Water Dimer Molecules

A quantum-mechanics molecular-mechanics scheme for extended systems

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