The reaction field of a water molecule in liquid water: Comparison of different quantum/classical models

Chalmet, Stéphanie; Ruiz‐López, Manuel F.

doi:10.1063/1.1389094

Cited by 39 publications

(34 citation statements)

References 66 publications

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“…As hydrogen bonds are involved it is expected that the OH distances of the central molecule should slightly increase. This increase has been estimated previously [6,10] to be within 0.002 and 0.013 A A, with large statistical errors. Slight change in the water geometry by increasing both OH distances by 0.01 A A in the MP2/aug-cc-pVDZ level has led to an increase in the dipole moment by only 0.005 D (from 1.861 to 1.866 D).…”

Section: Discussionmentioning

confidence: 86%

“…The results of Table 3 indicate that there is a large polarization in liquid water with molecules as far as 10 A A still affecting the calculated dipole. We now focus in the change of the MP2/aug-cc-pVQZ results with the number of polarizing molecules.…”

Section: Extrapolation and Statistical Convergencementioning

confidence: 90%

“…Whereas in the gas phase the dipole moment of water has a conclusive value of 1.855 D [18], in the liquid phase its precise dipole moment value has been subjected to some debate. Several previous [2][3][4][5][6][7][8][9][10][11][12][13][14][15] theoretical studies have predicted dipole changes from 0.3 D to a larger change of 1.1 D in going from the gas to the liquid phase. Recent estimates include the ab initio second-order result by Tu and Laaksonen [12] Silvestrelli and Parrinello [6] estimated a very large change leading to a value of 3.0 D. There are two aspects related to large values for the dipole moment of the liquid.…”

Section: Introductionmentioning

confidence: 99%

“…Theoretical estimates [2][3][4][5][6][7][8][9][10][11][12][13][14][15] predict this increase to lie between 15% and 60%. Although the experimental measurement of the dipole moment in liquid water is not possible, the precise value of this dipole moment is a true theoretical challenge and has attracted so much attention [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. Whereas in the gas phase the dipole moment of water has a conclusive value of 1.855 D [18], in the liquid phase its precise dipole moment value has been subjected to some debate.…”

Section: Introductionmentioning

confidence: 99%

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Electronic polarization of liquid water: converged Monte Carlo-quantum mechanics results for the multipole moments

Coutinho

Guedes

Cabral

et al. 2003

Chemical Physics Letters

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Sequential Monte Carlo/Quantum Mechanical (S-MC/QM) calculations of the dipole moment of liquid water using extensive and different quantum chemical methods and statistically converged results give an induced dipole moment of 0:74 AE 0:14 D. This corresponds to a dipole moment of liquid water of 2:60 AE 0:14 D, in excellent agreement with the value derived from the dielectric constant and other previous theoretical estimates. Change in multipole moments are also reported using statistically converged MP2/aug-cc-pVQZ calculations.

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Section: Discussionmentioning

confidence: 86%

Section: Extrapolation and Statistical Convergencementioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Electronic polarization of liquid water: converged Monte Carlo-quantum mechanics results for the multipole moments

Coutinho

Guedes

Cabral

et al. 2003

Chemical Physics Letters

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“…They are closer to 0.75 D, the lower limit estimated from Coulson and Eisenberg's data, 91 than to 1.24 D from data of Batista et al 103 A wide range of values for the induced dipole moment have been reported from ab initio or combined QM/MM calculations. 102,105,110 Compared to the COS/B2 model, the COS/G2 and COS/G3 models improve the infinite system Kirkwood factor g K . The Debye dielectric relaxation time D gives an estimate of the relaxation time of the hydrogen bond network and we expect that the COS/G2 and COS/G3 models mimic the hydrogen bond network more properly than the COS/B2 model.…”

Section: B Liquid Water At Room Temperature and Pressurementioning

confidence: 99%

Charge-on-spring polarizable water models revisited: From water clusters to liquid water to ice

Yu¹,

Gunsteren²

2004

The Journal of Chemical Physics

197

234

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The properties of two improved versions of charge-on-spring �COS� polarizable water models (COS/G2 and COS/G3) that explicitly include nonadditive polarization effects are reported. In COS models, the polarization is represented via a self-consistently induced dipole moment consisting of a pair of separated charges. A previous polarizable water model (COS/B2), upon which the improved versions are based, was developed by Yu, Hansson, and van Gunsteren �J. Chem. Phys. 118, 221 �2003��. To improve the COS/B2 model, which overestimated the dielectric permittivity, one additional virtual atomic site was used to reproduce the water monomer quadrupole moments besides the water monomer dipole moment in the gas phase. The molecular polarizability, residing on the virtual atomic site, and Lennard-Jones parameters for oxygen-oxygen interactions were varied to reproduce the experimental values for the heat of vaporization and the density of liquid water at room temperature and pressure. The improved models were used to study the properties of liquid water at various thermodynamic states as well as gaseous water clusters and ice. Overall, good agreement is obtained between simulated properties and those derived from experiments and ab initio calculations. The COS/G2 and COS/G3 models may serve as simple, classical, rigid, polarizable water models for the study of organic solutes and biopolymers. Due to its simplicity, COS type of polarization can straightforwardly be used to introduce explicit polarization into (bio)molecular force fields. The properties of two improved versions of charge-on-spring ͑COS͒ polarizable water models (COS/G2 and COS/G3) that explicitly include nonadditive polarization effects are reported. In COS models, the polarization is represented via a self-consistently induced dipole moment consisting of a pair of separated charges. A previous polarizable water model (COS/B2), upon which the improved versions are based, was developed by Yu, Hansson, and van Gunsteren ͓J. Chem. Phys. 118, 221 ͑2003͔͒. To improve the COS/B2 model, which overestimated the dielectric permittivity, one additional virtual atomic site was used to reproduce the water monomer quadrupole moments besides the water monomer dipole moment in the gas phase. The molecular polarizability, residing on the virtual atomic site, and Lennard-Jones parameters for oxygen-oxygen interactions were varied to reproduce the experimental values for the heat of vaporization and the density of liquid water at room temperature and pressure. The improved models were used to study the properties of liquid water at various thermodynamic states as well as gaseous water clusters and ice. Overall, good agreement is obtained between simulated properties and those derived from experiments and ab initio calculations. The COS/G2 and COS/G3 models may serve as simple, classical, rigid, polarizable water models for the study of organic solutes and biopolymers. Due to its simplicity, COS type of polarization can straightforwardly be used to introduce explicit ...

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The Effect of Electric Fields on Oxidization Processes at the Air‐Water Interface

Martins‐Costa,

Ruiz‐López

2024

Angewandte Chemie

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At the air‐water interface, many reactions are accelerated, sometimes by several orders of magnitude. This phenomenon has proved to be particularly important in water microdroplets, where the spontaneous oxidation of many species stable in bulk has been experimentally demonstrated. Different theories have been proposed to explain this finding, but it is currently believed that the role of interfacial electric fields is key. In this work, we have carried out a quantum chemistry study aimed at shedding some light on this question. We have studied two prototypical processes in which a hydroxide anion transfers its excess electron to either the water environment or a dioxygen molecule. To model the interface, we use a cluster of 21 water molecules immersed in an electric field, and we examine the energetics of the studied reactions as a function of field magnitude. Our results reveal that electric fields close to those estimated for the neat air‐water interface (~0.15 V×Å‐1) have a moderate effect on the reaction energetics and that much stronger fields (>1 V×Å‐1) are required to get spontaneous electron transfer. Therefore, the study suggests that additional factors such as an excess charge in microdroplets need to be considered for explaining the experimental observations.

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The reaction field of a water molecule in liquid water: Comparison of different quantum/classical models

Abstract: Electric-field-controlled water and ion permeation of a hydrophobic nanopore Potentials of mean force of simple ions in ambient aqueous solution. II. Solvation structure from the threedimensional reference interaction site model approach, and comparison with simulations

Cited by 39 publications

References 66 publications

Electronic polarization of liquid water: converged Monte Carlo-quantum mechanics results for the multipole moments

Electronic polarization of liquid water: converged Monte Carlo-quantum mechanics results for the multipole moments

Charge-on-spring polarizable water models revisited: From water clusters to liquid water to ice

The Effect of Electric Fields on Oxidization Processes at the Air‐Water Interface

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