A transferable classical potential for the water molecule

We developed a new model for the water molecule which contains only three Gaussian charges. Using the gas-phase geometry the dipole moment of the molecule matches, the quadrupole moment closely approximates the experimental values. The negative charge is connected by a harmonic spring to its gas-phase position. The polarized state is identified by the equality of the intermolecular electrostatic force and the spring force acting on the negative charge. In each timestep the instantaneous position of the massless negative charge is determined by iteration. Using the technique of Ewald summation, we derived expressions for the potential energy, the forces, and the pressure for Gaussian charges. The only properties to be fitted are the half-width values of the Gaussian charge distributions and the parameters of the nonelectrostatic repulsion-attraction potential. We determined the properties of gas-phase clusters up to six molecules, the internal energy and density of ambient water and hexagonal ice. We calculated the equilibrium density of ice VII as a function of pressure. As an additional test, we calculated the pair-correlation function, the isotherm compressibility, the heat capacity, and the self-diffusion coefficients for ambient water. As far as we know, this is the first classical model of water which is able to estimate both ends of the phase diagram, the high pressure ice VII, and the gas clusters of water with excellent accuracy.     

Polarizable model of water with field-dependent polarization

The polarizable charge-on-spring model of water with three Gaussian charges developed by the present authors [A. Baranyai and P. T. Kiss, J. Chem. Phys. 133, 144109 (2010)] was studied. We introduced an analytic function for the polarizability in terms of the local electric field. Following theoretical suggestions, the polarizability decreases from its experimental gas-phase value, in our approach, toward a high-field threshold. Using this modified polarizability, we reparameterized the model by calculating its dielectric constant and obtained good estimates of density and internal energy for ambient water, hexagonal ice, and water cluster properties. Mimicked by the new model, we studied liquid water under the impact of homogeneous static electric field in the rage of 0-2.5 V/?. Both the density and the average dipole moment increase with the strength of the electric field. However, the internal energy shows a minimum at ~0.35 V/?. At this field strength, the model starts ordering into a crystal structure. At higher fields the liquid forms a crystalline structure which is a special version of cubic ice.     

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

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. 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.     

Electrostatic calculation of linear and non-linear optical properties of ice Ih,II, IX and VIII

Macroscopic first- and third-order susceptibilities of ice Ih, ice II, ice IX and ice VIII are calculated using static and frequency-dependent electronic and static vibrational molecular (hyper)polarizabilities at the MP2 level. The molecular properties are in good agreement with experiment and with high-level ab initio calculations. Intermolecular electrostatic and polarization effects due to induced dipoles are taken into account using a rigorous local-field theory. The electric field due to permanent dipoles is used to calculate effective in-crystal (hyper)polarizabilities. The polarizability depends only weakly on the permanent field, but the dipole moment and the hyperpolarizabilities are strongly affected. The calculated linear susceptibility is in good agreement with available experimental data for ice Ih, and the third-order susceptibility for a third harmonic generation experiment is in reasonable agreement with experimental values for liquid water. The molecular vibrational contributions have a small effect on the susceptibilities. The electric properties of a water tetramer are calculated and used to estimate the effect of non-dipolar interactions on the susceptibilities of ice Ih, which are found to be small.     

Transferable model of water with variable molecular size

By decreasing the steepness of the repulsive wing in the intermolecular potential, one can extend the applicability of a water model to the high pressure region. Exploiting this trivial possibility, we published a polarizable model of water which provided good estimations not only of gas clusters, ambient liquid, hexagonal ice, but ice VII at very high pressures as well [A. Baranyai and P. Kiss, J. Chem. Phys. 133, 144109 (2010)]. This straightforward method works well provided the closest O-O distance is reasonably shorter in the high pressure phase than in hexagonal ice. If these O-O distances are close to each other and we fit the interactions to obtain an accurate picture of hexagonal ice, we underestimate the density of the high-pressure phases. This can be overcome if models use contracted molecules under high external pressure.In this paper we present a method, which is capable to describe the contraction of water molecules under high pressure by using two simple repulsion-attraction functions. These functions represent the dispersion interaction under low pressure and high pressure. The switch function varies between 0 and 1 and portions the two repulsions among the individual particles. The argument of the switch function is a virial-type expression, which can be interpreted as a net force compressing the molecule. We calculated the properties of gas clusters, densities, and internal energies of ambient water, hexagonal ice, ice III, ice VI, and ice VII phases and obtained excellent match of experimental data.     

Static dielectric constants and molecular dipole distributions of liquid water and ice-Ih investigated by the PAW-PBE exchange-correlation functional

The static dielectric constants, ε(s), of ice-Ih and liquid water were calculated using density functional theory with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional and the projector-augmented-wave (PAW) approach. Proton disordered ice configurations and uncorrelated liquid configurations were sampled with the electrostatic switching method using force fields specially designed to facilitate the ab initio free energy perturbation calculations. Our results indicate that PAW-PBE underestimates the ε(s) of both ice-Ih and liquid water but predicts the ratio of ice and water ε(s) in good agreement with experimental measurements. PAW-PBE gives average water dipole moments of 2.50 D in ice-Ih and 2.48 D in the liquid. Our results show that the fixed-charge water models developed by adaptive force matching can reproduce the PAW-PBE dipole moments with an error of approximately 5%. The ice and liquid models created in this work have polarizabilities of 1.32 ?(3) and 1.30 ?(3), respectively, along the HOH bisector direction.     

On the performance of molecular polarization methods. I. Water and carbon tetrachloride close to a point charge

The three main methods to implement molecular polarization (point dipoles, fluctuating charges, and shell model) are tested against high level ab initio calculations for a molecule (water, carbon tetrachloride) close to a point charge (at the distance of a lithium or magnesium ion). The goal is to check whether an approximation (linear polarization) strictly valid at large intermolecular distances is sufficiently accurate for liquid state molecular dynamics simulations, where strong polarization effects are to be expected at short separations. The monitored observable is the molecular dipole moment as a function of the charge-molecule distance for selected molecular orientations. Analytic formulas are derived for the components of the molecular polarization tensor, facilitating the optimization of the performance for each polarization method as a function of its underlying parameters. Overall, the methods studied provide a remarkably good representation of the induced dipole, with no divergences appearing even at the shortest distances. For water close to a monovalent point charge the point dipole model, implemented with one or three dipoles, accurately reproduces the water dipole moment at all distances. Deficiencies appear as the molecular polarizability and/or charge increase: basically, the ab initio induced moments grow faster at intermediate distances than the linear increase characteristic of the phenomenological polarization methods, suggesting that nonlinear effects (hyperpolarizability) cannot be neglected in these cases. Regarding the capabilities of each method, the point dipole method is the one that performs best overall, with the shell model achieving acceptable results in most instances. The fluctuating charge method shows some noticeable limitations for implementations of comparable complexity (in terms of the number of sites required).     

On the performance of molecular polarization methods. II. Water and carbon tetrachloride close to a cation

Our initial study on the performance of molecular polarization methods close to a positive point charge [M. Masia, M. Probst, and R. Rey, J. Chem. Phys. 121, 7362 (2004)] is extended to the case in which a molecule interacts with a real cation. Two different methods (point dipoles and shell model) are applied to both the ion and the molecule. The results are tested against high-level ab initio calculations for a molecule (water or carbon tetrachloride) close to Li+, Na+, Mg2+, and Ca2+. The monitored observable is in all cases the dimer electric dipole as a function of the ion-molecule distance for selected molecular orientations. The moderate disagreement previously obtained for point charges at intermediate distances, and attributed to the linearity of current polarization methods (as opposed to the nonlinear effects evident in ab initio calculations), is confirmed for real cations as well. More importantly, it is found that at short separations the phenomenological polarization methods studied here substantially overestimate the dipole moment induced if the ion is described quantum chemically as well, in contrast to the dipole moment induced by a point-charge ion, for which they show a better degree of accord with ab initio results. Such behavior can be understood in terms of a decrease of atomic polarizabilities due to the repulsion between electronic charge distributions at contact separations. It is shown that a reparametrization of the Thole method for damping of the electric field, used in conjunction with any polarization scheme, allows to satisfactorily reproduce the dimer dipole at short distances. In contrast with the original approach (developed for intramolecular interactions), the present reparametrization is ion and method dependent, and corresponding parameters are given for each case.     

The bend angle of water in ice Ih and liquid water: The significance of implementing the nonlinear monomer dipole moment surface in classical interaction potentials

The implementation of the physically accurate nonlinear dipole moment surface of the water monomer in the context of the Thole-type, polarizable, flexible interaction potential results in the only classical potential, which, starting from the gas phase value for the bend angle (104.52 degrees), reproduces its experimentally observed increase in the ice Ih lattice and in liquid water. This is in contrast to all other classical potentials to date, which predict a decrease of the monomer bend angle in ice Ih and in liquid water with respect to the gas phase monomer value. Simulations under periodic boundary conditions of several supercells consisting of up to 288 molecules of water used to sample the proton disorder in the ice Ih lattice yield an average value of vartheta(HOH)(I(h))=108.4 degrees +/-0.2 degrees for the minimized structures (T=0 K) and 108.1 degrees +/-2.8 degrees at T=100 K. Analogous simulations for liquid water predict an average value of vartheta(HOH)(liquid)=106.3 degrees +/-4.9 degrees at T=300 K. The increase of the monomer bend angle of water in condensed environments is attributed to the use of geometry-dependent charges that are used to describe the nonlinear character of the monomer's dipole moment surface. Our results suggest a new paradigm in the development of classical interaction potential models of water that can be used to describe condensed aqueous environments.     

Microwave heating of water, ice, and saline solution: molecular dynamics study

In order to study the heating process of water by the microwaves of 2.5-20 GHz frequencies, the authors have performed molecular dynamics simulations by adopting a nonpolarizable water model that has fixed point charges on a rigid-body geometry. All runs are started from the equilibrated states derived from the I(c) ice with given density and temperature. In the presence of microwaves, the molecules of liquid water exhibit rotational motion whose average phase is delayed from the microwave electric field. Microwave energy is transferred to the kinetic and intermolecular energies of water, where one-third of the absorbed microwave energy is stored as the latter energy. The water in ice phase is scarcely heated by microwaves because of the tight hydrogen-bonded network of water molecules. Dilute salt water is significantly more heated than pure water because of the field-induced motion of salt ions, especially that of large-size ions, by the microwave electric field and energy transfer to water molecules by collisions.     

Quantum rigid dipole in a permanent electric field. II. Model of librational motion in liquid water and ice Ih: Preliminary results

A theoretical one-body model of librational motion in liquid water and ice Ih is proposed within the quantum mechanical treatment of a rigid and pointlike dipole in a permanent electric field and the concept of the internal electric field justified for V-structure of liquid water.     

Topological analysis of the molecular charge density and impact sensitivy models of energetic molecules

Important explosives of practical use are composed of nitroaromatic molecules. In this work, we optimized geometries and calculated the electron density of 17 nitroaromatic molecules using the Density Functional Theory (DFT) method. From the DFT one-electron density matrix, we computed the molecular charge densities, thus the electron densities, which were then decomposed into electric multipoles located at the atomic sites of the molecules using the distributed multipole analysis (DMA). The multipoles, which have a direct chemical interpretation, were then used to analyze in details the ground state charge structure of the molecules and to seek for correlations between charge properties and sensitivity of the corresponding energetic material. The DMA multipole moments do not present large variations when the size of the Gaussian basis set is changed; the largest variations occurred in the range 10-15% for the dipole and quadrupole moments of oxygen atoms. The charges on the carbon atoms of the aromatic ring of each molecule become more positive when the number of nitro groups increases and saturate when there are five and six nitro groups. The magnitude and the direction of the dipole moments of the carbon atoms, indicators of site polarization, also depend on the nature of adjacent groups, with the largest dipole value being for C-H bonds. The total magnitude of the quadrupole moment of the aromatic ring carbon atoms indicates a decrease in the delocalized electron density due to an electron-withdrawing effect. Three models for sensitivity of the materials based on the DMA multipoles were proposed. Explosives with large delocalized electron densities in the aromatic ring of the component molecule, expressed by large quadrupole values on the ring carbon atoms, correspond to more insensitive materials. Furthermore, the charges on the nitro groups also influence the impact sensitivity.     

Grand canonical monte carlo simulation study of water adsorption in silicalite at 300 K

This molecular simulation work focuses on the adsorption of water in a priori hydrophobic silicalite-1, a microporous ordered silica. The water-water interactions are described with the SPC model, while water-silica interactions are calculated in the framework of the PN-TrAZ model. The water adsorption isotherm at 300 K, the configurational energies, and the isosteric heat of adsorption are calculated by the grand canonical Monte Carlo (GCMC) simulation method. The thermodynamic integration scheme allows one to calculate the grand potential along the adsorption isotherm. The adsorption results are compared with experiments, showing only qualitative agreement. Indeed, the simulations do not reproduce the expected hydrophobicity of silicalite (Eroshenko, V.; Regis, R.-C.; Soulard, M.; Patarin, J. C. R. Phys. 2002, 3, 111). This indicates that common models used to describe confined polar molecules are far from being operative. In this work, it is shown, on the basis of periodic ab initio calculations, that confined water molecules in silicalite have a dipole value roughly 10% smaller than that in the bulk liquid phase, indicating that the environment felt by a confined water molecule in silicalite pores is not equivalent to that in the bulk liquid. This suggests that effective intermolecular potentials parametrized for bulk water are inefficient to describe ultraconfined water molecules. Reducing the SPC water dipole moment by 5% (i.e., decreasing water partial charges in magnitude) in GCMC calculations does allow reproducing the experimental water/silicalite isotherm at 300 K.     

Semiempirical self-consistent polarization description of bulk water, the liquid-vapor interface, and cubic ice

We have applied an efficient electronic structure approach, the semiempirical self-consistent polarization neglect of diatomic differential overlap (SCP-NDDO) method, previously parametrized to reproduce properties of water clusters by Chang, Schenter, and Garrett [ J. Chem. Phys. 2008 , 128 , 164111 ] and now implemented in the CP2K package, to model ambient liquid water at 300 K (both the bulk and the liquid-vapor interface) and cubic ice at 15 and 250 K. The SCP-NDDO potential retains its transferability and good performance across the full range of conditions encountered in the clusters and the bulk phases of water. In particular, we obtain good results for the density, radial distribution functions, enthalpy of vaporization, self-diffusion coefficient, molecular dipole moment distribution, and hydrogen bond populations, in comparison to experimental measurements.     

不同疏水基表面活性剂溶剂化的电子结构特征

用从头算法RHF／6-31G^*和Onsager溶剂模型分别优化了不同疏水端基表面活性剂阴离子溶剂化前后的几何构型,得到气态和溶剂化的总能量、电荷分布、偶极矩、极化能等．比较了它们溶剂化前后的构型变化和电子结构特征．在RHF／6-31G^*平台上探讨了不同疏水端基影响阴离子表面活性剂表面张力的内在原因．     

Toward a consistent treatment of polarization in model QM/MM calculations

The concept of model chemistries within hybrid QM/MM calculations has been addressed through analysis of the polarization energy determined by two distinct approaches based on (i) induced charges and (ii) induced dipoles. The quantum mechanical polarization energy for four configurations of the water dimer has been determined for a range of basis sets using Morokuma energy decomposition analysis. This benchmark value has been compared to the fully classical polarization energy determined using the induced dipole approach, and the molecular mechanics polarization energy calculated using induced charges within the MM region of hybrid QM/MM calculations. From the water dimer calculations, it is concluded that the induced charge approach is consistent with medium sized basis set calculations whereas the induced dipole approach is consistent with large basis set calculations. This result is highly relevant to the concept of QM/MM model chemistries.     

Solvent effects on the UV-visible absorption spectrum of benzophenone in water: a combined Monte Carlo quantum mechanics study including solute polarization

The entire ultraviolet-visible absorption spectrum of benzophenone in water is studied and compared with the same spectrum in gas phase. Five transitions are considered, and the corresponding solvatochromic shifts are obtained and compared to experiment. Using a sequential procedure of Monte Carlo simulations and quantum mechanical calculations, liquid configurations were generated and an averaged spectrum of the solution was calculated. The solute polarization was included by an iterative procedure where the atomic charges of the solute were obtained as an average with the solvent distribution. The calculated average dipole moment of benzophenone in water, with MP26-31++G(d,p), converges to the value of 5.84+/-0.05 D, 88% larger than the gas-phase value of 3.11 D. Using 100 statistically uncorrelated configurations and solvation shells with 235 explicit water molecules selected by a minimum-distance distribution of solvent shells, instead of the usual radial distribution, the excitation energies were obtained from solute-solvent all-valence-electron INDO/CIS calculations. The shift of the weak n-pi(*) transition is obtained as 2045+/-40 cm(-1) and the strong and broad pi-pi(*) shift as -1790+/-30 cm(-1). These results are in good agreement with the experimental values of 2200 and -1600 cm(-1), respectively. Standard procedure used by common force fields to generate atomic charges to describe the electrostatic moments of the solute, with HF6-31G(d), gives a dipole moment of 3.64 D. Using these standard charges in the simulation, the average shifts are calculated as 1395+/-35 and -1220+/-25 cm(-1), both about 600 cm(-1) smaller in magnitude than those obtained with the average converged fully polarized solute. The influence of the solute polarization in the solute-solvent interaction and, in particular, in solute-solvent hydrogen bonds is analyzed.     

A classical polarizable model for simulations of water and ice

We develop a classical rigid polarizable model of water for molecular simulations of water and ice. The model uses the Rowlinson five-site geometry: oxygen bearing the Lennard-Jones interaction and linearly polarizable point dipole, two positively charged hydrogens, and two massless negative charges placed symmetrically off oxygen so that the experimental dipole moment is reproduced. The target properties are the densities of water and ice Ih, diffusivity, enthalpies of fusion and vaporization, and the ice Ih melting point. The surface tension at lower temperatures is by 7% underestimated whereas the dielectric constant by 6% overestimated. Diffusivity and viscosity worsen at higher temperatures, although the Stokes radius is overestimated only by 2-7%. The ice Ih melting temperature is 260 K and the temperature of maximum density is 269 K. Rescaling the charges by a factor of 1.01 and Lennard-Jones energy by 1.0201 improves the melting point and energy-related quantities but shifts the agreement of kinetic properties to higher temperatures. For the model we propose abbreviation POL4D.