Dynamical properties of the soft sticky dipole-quadrupole-octupole water model: a molecular dynamics study

The dynamical properties of the soft sticky dipole-quadrupole-octupole (SSDQO) water model using SPC/E moments are calculated utilizing molecular dynamics simulations. This new potential for liquid water describes the water-water interactions by a Lennard-Jones term and a sticky potential, which is an approximate moment expansion with point dipole, quadrupole, and octupole moments, and reproduces radial distribution functions of pure liquid water using the moments of SPC/E [Ichiye and Tan, J. Chem. Phys. 124, 134504 (2006)]. The forces and torques of SSDQO water for the dipole-quadrupole, quadrupole-quadrupole, and dipole-octupole interactions are derived here. The simulations are carried out at 298 K in the microcanonical ensemble employing the Ewald method for the long-range dipole-dipole interactions. Here, various dynamical properties associated with translational and rotational motions of SSDQO water using the moments of SPC/E (SSDQO:SPC/E) water are compared with the results from SPC/E and also experiment. The self-diffusion coefficient of SSDQO:SPC/E water is found to be in excellent agreement with both SPC/E and experiment whereas the single particle orientational relaxation time for dipole vector is better than SPC/E water but it is somewhat smaller than experiment. The dielectric constant of SSDQO:SPC/E is essentially identical to SPC/E, and both are slightly lower than experiment. Also, molecular dynamics simulations of the SSDQO water model are found to be about twice as fast as three-site models such as SPC/E.     

Study of multipole contributions to the structure of water around ions in solution using the soft sticky dipole-quadrupole-octupole (SSDQO) model of water

The solvation of ions in the soft sticky dipole-quadrupole-octupole (SSDQO) model for liquid water is presented here. This new potential energy function for liquid water describes water-water interactions by a Lennard-Jones term plus a sticky potential consisting of an approximate moment expansion with point dipole, quadrupole, and octupole moments. The SSDQO potential energy function using the moments from extended simple point charge (SPC/E), TIP3P, or TIP5P reproduces the pair potential energy functions and radial distribution functions of the respective multipoint model but it is much faster than even the three-point models. Here, the solvation of ions in SSDQO water is studied using ion-water potential energy functions consisting of moment expansions up to the charge-quadrupole term, up to the charge-octupole term, and up to an approximate charge-hexadecapole term using the moments of SPC/E water. The radial distributions from Monte Carlo simulations show the best agreement with the results for ions in SPC/E water for the expansion up to the charge-hexadecapole term. Thus, the best results are obtained when the water-water and ion-water potentials are exact up to the 1r(4) term and also contain an approximate 1r(5) term. Overall, the simplicity, efficiency, and accuracy of the SSDQO potential make it potentially very useful for computer simulations of aqueous solvation.     

Soft sticky dipole-quadrupole-octupole potential energy function for liquid water: an approximate moment expansion

A new, efficient potential energy function for liquid water is presented here. The new model, which is referred here as the soft sticky dipole-quadrupole-octupole (SSDQO) model, describes a water molecule as a Lennard-Jones sphere with point dipole, quadrupole, and octupole moments. It is a single-point model and resembles the hard-sphere sticky dipole potential model for water by Bratko et al. [J. Chem. Phys. 83, 6367 (1985)] and the soft sticky dipole model by Ichiye and Liu [J. Phys. Chem. 100, 2723 (1996)] except now the sticky potential consists of an approximate moment expansion for the dimer interaction potential, which is much faster than the true moment expansion. The object here is to demonstrate that the SSDQO potential energy function can accurately mimic the potential energy function of a multipoint model using the moments of that model. First, the SSDQO potential energy function using the dipole, quadruple, and octupole moments from SPC/E, TIP3P, or TIP5P is shown to reproduce the dimer potential energy functions of the respective multipoint model. In addition, in Monte Carlo simulations of the pure liquid at room temperature, SSDQO reproduces radial distribution functions of the respective model. However, the Monte Carlo simulations using the SSDQO model are about three times faster than those using the three-point models and the long-range interactions decay faster for SSDQO (1/r(3) and faster) than for multipoint models (1/r). Moreover, the contribution of each moment to the energetics and other properties can be determined. Overall, the simplicity, efficiency, and accuracy of the SSDQO potential energy function make it potentially very useful for studies of aqueous solvation by computer simulations.     

Solvation of Glucose, Trehalose, and Sucrose by the Soft Sticky Dipole-Quadrupole-Octupole Water Model

Water structure around sugars modeled by partial charges is compared for soft-sticky dipole-quadrupole-octupole (SSDQO), a fast single-site multipole model, and commonly used multi-site models in Monte Carlo simulations. Radial distribution functions and coordination numbers of all the models indicate similar hydration by hydrogen-bond donor and acceptor waters. However, the new optimized SSDQO1 parameters as well as TIP4P-Ew and TIP5P predict a "lone-pair" orientation for the water accepting the sugar hydroxyl hydrogen bond that is more consistent with the limited experimental data than the "dipole" orientation in SPC/E, which has important implications for studies of the cryoprotectant properties of sugars.     

UNDERSTANDING STRUCTURAL EFFECTS OF MULTIPOLE MOMENTS ON AQUEOUS SOLVATION OF IONS USING THE SOFT-STICKY DIPOLE-QUADRUPOLE-OCTUPOLE WATER MODEL

The effects of water multipole moments on the aqueous solvation of ions were determined in Monte Carlo simulations using soft-sticky dipole-quadrupole-octupole (SSDQO) water. Water molecules formed linear hydrogen bonds to Cl(-) using the new SSDQO1 parameters, similar to multi-site models. However, the dipole vector was tilted rather than parallel to the oxygen-Na(+) internuclear vector as in most multi-site model, while experiment and ab initio molecular dynamics simulations generally indicate a range of values between tilted and parallel. By varying the multipoles in SSDQO, the octupole was found to determine the orientation around Na(+). Moreover, analysis of the multipoles of more conventional models is predictive of their performance as solvents.     

Hydroxyl radical in aqueous solution: Computer simulation

Molecular dynamics simulations of hydroxyl radical in water are carried out by use of a classical simple point charge extended (SPC/E) water model and a similar point charge model for hydroxyl radical. Structural and dynamical properties are studied along the coexistence curve of SPC/E water at 298, 373, 473, 573, and 633 K and above its critical point at 683, 733, 783, and 833 K with density fixed at 0.3 g/cm3. Dramatic changes in the diffusion dynamics of water and hydroxyl radical near the critical point are related to the reorganization of the three-dimensional structure of water around hydroxyl radical, as revealed by the study of the spatial distribution functions. This study helps us understand the kinetics of oxidation reactions in high-temperature water.     

Influence of bond flexibility on the vapor-liquid phase equilibria of water

The authors performed Gibbs ensemble simulations on the vapor-liquid equilibrium of water to investigate the influence of incorporating intramolecular degrees of freedom in the simple point charge (SPC) water model. Results for vapor pressures, saturation densities, heats of vaporization, and the critical point for two different flexible models are compared with data for the corresponding rigid SPC and SPC/E models. They found that the introduction of internal vibrations, and also their parametrization, has an observable effect on the prediction of the vapor-liquid coexistence curve. The flexible SPC/Fw model, although optimized to describe bulk diffusion and dielectric constants at ambient conditions, gives the best prediction of saturation densities and the critical point of the examined models.     

Accurate thermodynamic and dielectric equations of state for high-temperature simulated water

The thermodynamic and dielectric properties of the simple point charge extended (SPC/E) water model are examined over wide temperature and density range by means of molecular dynamic simulations. Accurate analytical thermodynamic and dielectric equations of state for the SPC/E pair-potential are presented. Parameterizations cover a broad range of high temperature states including the critical region. The critical point parameters of SPC/E water were determined to be ρ_c = 0.276 g/cm³, T_c = 640.25 K and p_c = 164.37 bar. The value of the static dielectric constant of SPC/E water at its critical point was calculated to be 5.35, which compares remarkably well with the corresponding experimental value of 5.36. Analytical thermodynamic and dielectric equations for the saturated liquid and vapor densities are also given.     

Effects of water model and simulation box size on protein diffusional motions

We performed molecular dynamics simulations of ubiquitin with the distinct water models, TIP3P, SPC, SPC/E, and SPC/Fw, in different system sizes with different box shapes. The translational diffusion constants of pure water linearly depend on the effective box length, which is known as finite size effect, whereas the first and second rotational times of pure water are nearly constant. We then observed that both the overall translation and rotational motions of the protein are linearly correlated to the viscosity of pure water. As expected from the finite size effect in pure water, the translational diffusion of the protein is significantly affected by the system size, and rotational diffusion is nearly size-independent. After correction for the finite size effect, the SPC/E and SPC/Fw models reproduce both the translational and rotational motion of the protein relatively well. Thus, water models that reproduce the experimentally derived diffusional properties of pure water accurately are expected to also be suitable for simulating protein diffusion quantitatively.     

The melting temperature of the most common models of water

The melting temperature of ice I(h) for several commonly used models of water (SPC, SPC/E,TIP3P,TIP4P, TIP4P/Ew, and TIP5P) is obtained from computer simulations at p = 1 bar. Since the melting temperature of ice I(h) for the TIP4P model is now known [E. Sanz, C. Vega, J. L. F. Abascal, and L. G. MacDowell, Phys. Rev. Lett. 92, 255701 (2004)], it is possible to use the Gibbs-Duhem methodology [D. Kofke, J. Chem. Phys. 98, 4149 (1993)] to evaluate the melting temperature of ice I(h) for other potential models of water. We have found that the melting temperatures of ice I(h) for SPC, SPC/E, TIP3P, TIP4P, TIP4P/Ew, and TIP5P models are T = 190 K, 215 K, 146 K, 232 K, 245 K, and 274 K, respectively. The relative stability of ice I(h) with respect to ice II for these models has also been considered. It turns out that for SPC, SPC/E, TIP3P, and TIP5P the stable phase at the normal melting point is ice II (so that ice I(h) is not a thermodynamically stable phase for these models). For TIP4P and TIP4P/Ew, ice I(h) is the stable solid phase at the standard melting point. The location of the negative charge along the H-O-H bisector appears as a critical factor in the determination of the relative stability between the I(h) and II ice forms. The methodology proposed in this paper can be used to investigate the effect upon a coexistence line due to a change in the potential parameters.     

Relation between the melting temperature and the temperature of maximum density for the most common models of water

Water exhibits a maximum in density at normal pressure at 4 degrees above its melting point. The reproduction of this maximum is a stringent test for potential models used commonly in simulations of water. The relation between the melting temperature and the temperature of maximum density for these potential models is unknown mainly due to our ignorance about the melting temperature of these models. Recently we have determined the melting temperature of ice I(h) for several commonly used models of water (SPC, SPC/E, TIP3P, TIP4P, TIP4P/Ew, and TIP5P). In this work we locate the temperature of maximum density for these models. In this way the relative location of the temperature of maximum density with respect to the melting temperature is established. For SPC, SPC/E, TIP3P, TIP4P, and TIP4P/Ew the maximum in density occurs at about 21-37 K above the melting temperature. In all these models the negative charge is located either on the oxygen itself or on a point along the H-O-H bisector. For the TIP5P and TIP5P-E models the maximum in density occurs at about 11 K above the melting temperature. The location of the negative charge appears as a geometrical crucial factor to the relative position of the temperature of maximum density with respect to the melting temperature.     

A computational investigation of thermodynamics, structure, dynamics and solvation behavior in modified water models

We investigate the properties of geometrically modified water models by performing molecular dynamics simulations of perturbations of the extended simple point charge (SPC/E) model of water over a wide range of temperatures at 1 bar. The geometric modification consists of altering the H-O-H angle in SPC/E. The dipole moment is held constant by altering the O-H bond length, while the electrostatic charges are left unchanged. We find that a H-O-H angle of at least 100 degrees is necessary for the appearance of density anomalies and of solubility extrema with respect to temperature for small apolar solutes. We observe the occurrence of two incompatible types of structural order in these models: Tetrahedral, with waterlike translational order for bent models with H-O-H angles in excess of 100 degrees ; and linear, with Lennard-Jones-like orientationally averaged translational order for smaller H-O-H angles. Increasing the H-O-H angle causes the density to increase, while at the same time shifting waterlike anomalies to progressively higher temperatures. For bent models with H-O-H angle greater than SPC/E's, we observe arrest of translational motion at 300 K (115 degrees) and 330 K (120 degrees).     

Solubility of methane in water: the significance of the methane-water interaction potential

The influence of the methane-water interaction potential on the value of the Henry constant obtained from molecular dynamics simulations was investigated. The SPC, SPC/E, MSPC/E, and TIP3P potentials were used to describe water and the OPLS-UA and TraPPE potentials for methane. Nonbonding interactions between unlike atoms were calculated both with one of four mixing rules and with our new methane-water interaction potential. The Henry constants obtained from simulations using any of the mixing rules differed significantly from the experimental ones. Good agreement between simulation and experiment was achieved with the new potential over the whole temperature range.     

The melting point of ice Ih for common water models calculated from direct coexistence of the solid-liquid interface

In this work we present an implementation for the calculation of the melting point of ice I(h) from direct coexistence of the solid-liquid interface. We use molecular dynamics simulations of boxes containing liquid water and ice in contact. The implementation is based on the analysis of the evolution of the total energy along NpT simulations at different temperatures. We report the calculation of the melting point of ice I(h) at 1 bar for seven water models: SPC/E, TIP4P, TIP4P-Ew, TIP4P/ice, TIP4P/2005, TIP5P, and TIP5P-E. The results for the melting temperature from the direct coexistence simulations of this work are in agreement (within the statistical uncertainty) with those obtained previously by us from free energy calculations. By taking into account the results of this work and those of our free energy calculations, recommended values of the melting point of ice I(h) at 1 bar for the above mentioned water models are provided.     

A novel approach for designing simple point charge models for liquid water with three interaction sites

A simultaneous improvement of the diffusion and dielectric properties of the simple point charge (SPC) model for liquid water appears to be very difficult with conventional reparametrization of the commonly used Lennard-Jones and Coulomb interaction functions and without including a self-energy correction in the effective pair-potential as is done in the SPC/E model. Here, a different approach to circumvent this problem is presented. A short-range interaction term, which corrects the oxygen-oxygen energy at small distances by small amounts of energy, was introduced in the nonbonded interaction function. This additional force-field term allows to derive new parameter sets for SPC-like water models that yield better agreement with experimental data on liquid water. Based on previous investigations of the force-field parameter dependence of the water properties of SPC-like models, the necessary parameter changes to obtain a lower diffusion coefficient and a larger dielectric permittivity were specified and accordingly six new models were developed. They all represent an improvement over SPC in terms of structural and diffusional properties, four of them show better dielectric properties also. One model, SPC/S, has been characterized in more detail, and represents most properties of liquid water better than SPC while avoiding the larger discrepancies with experimental values regarding density, thermal compressibility, energy, and free energy of the SPC/E model. We conclude that the use of a simple, short-ranged additional oxygen-oxygen interaction term makes a simultaneous improvement of the diffusion coefficient and the dielectric properties of water feasible.     

Assessment of biomolecular force fields for molecular dynamics simulations in a protein crystal

Different biomolecular force fields (OPLS‐AA, AMBER03, and GROMOS96) in conjunction with SPC, SPC/E and TIP3P water models are assessed for molecular dynamics simulations in a tetragonal lysozyme crystal. The root mean square deviations for the C_a atoms of lysozymes are about 0.1 to 0.2 nm from OPLS‐AA and AMBER03, smaller than 0.4 nm from GROMOS96. All force fields exhibit similar pattern in B‐factors, whereas OPLS‐AA and AMBER03 accurately reproduce experimental measurements. Despite slight variations, the primary secondary structures are well conserved using different force fields. Water diffusion in the crystal is approximately ten‐fold slower than in bulk phase. The directional and average water diffusivities from OPLS‐AA and AMBER03 along with SPC/E model match fairly well with experimental data. Compared to GROMOS96, OPLS‐AA and AMBER03 predict larger hydrophilic solvent‐accessible surface area of lysozyme, more hydrogen bonds between lysozyme and water, and higher percentage of water in hydration shell. SPC, SPC/E and TIP3P water models have similar performance in most energetic and structural properties, but SPC/E outperforms in water diffusion. While all force fields overestimate the mobility and electrical conductivity of NaCl, a combination of OPLS‐AA for lysozyme and the Kirkwood‐Buff model for ions is superior to others. As attributed to the steric restraints and surface interactions, the mobility and conductivity in the crystal are reduced by one to two orders of magnitude from aqueous solution. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Combined electronic structure/molecular dynamics approach for ultrafast infrared spectroscopy of dilute HOD in liquid H2O and D2O

We present a new approach that combines electronic structure methods and molecular dynamics simulations to investigate the infrared spectroscopy of condensed phase systems. This approach is applied to the OH stretch band of dilute HOD in liquid D2O and the OD stretch band of dilute HOD in liquid H2O for two commonly employed models of water, TIP4P and SPC/E. Ab initio OH and OD anharmonic transition frequencies are calculated for 100 HOD x (D2O)n and HOD x(H2O)n (n = 4-9) clusters randomly selected from liquid water simulations. A linear empirical relationship between the ab initio frequencies and the component of the electric field from the solvent along the bond of interest is developed. This relationship is used in a molecular dynamics simulation to compute frequency fluctuation time-correlation functions and infrared absorption line shapes. The normalized frequency fluctuation time-correlation functions are in good agreement with the results of previous theoretical approaches. Their long-time decay times are 0.5 ps for the TIP4P model and 0.9 ps for the SPC/E model, both of which appear to be somewhat too fast compared to recent experiments. The calculated line shapes are in good agreement with experiment, and improve upon the results of previous theoretical approaches. The methods presented are simple, and transferable to more complicated systems.     

Effects of the cutoff center on the mean potential and pair distribution functions in liquid water

Molecular dynamics simulations of extended simple point charge (SPC/E) water have been performed to study the effects of the truncation of long-range interactions on some calculated bulk properties of the liquid. The mean potential calculated in liquid water is sensitive to the choice of the cutoff center in the water molecule. The pair distribution function is also dependent on this choice, although not as strongly as the mean potential. An analysis is carried out to understand the origin of these effects. A common cutoff center is at the oxygen atom in the water molecule, but our study shows that this choice does not yield a mean potential value consistent with a more accurate estimate when no cutoff is applied. © 1995 John Wiley & Sons, Inc.     

Molecular dynamics simulations of water droplets on polymer surfaces

Molecular dynamics simulations were used to study the wetting of polymer surfaces with water. Contact angles of water droplets on crystalline and two amorphous polyethylene (PE) and poly(vinyl chloride) (PVC) surfaces were extracted from atomistic simulations. Crystalline surfaces were produced by duplicating the unit cell of an experimental crystal structure, and amorphous surfaces by pressing the bulk polymer step by step at elevated temperature between two repulsive grid surfaces to a target density. Different-sized water droplets on the crystalline PE surface revealed a slightly positive line tension on the order of 10(-12)-10(-11) N, whereas droplets on crystalline PVC did not yield a definite line tension. Microscopic contact angles produced by the simple point charge (SPC) water model were mostly a few degrees smaller than those produced by the extended SPC model, which, as the model with lowest bulk energy, presents an upper boundary for contact angles. The macroscopic contact angle for the SPC model was 94 degrees on crystalline PVC and 113 degrees on crystalline PE. Amorphicity of the surface increased the water contact angle on PE but decreased it on PVC, for both water models. If the simulated contact angles on crystalline and amorphous surfaces are combined in proportion to the crystallinity of the polymer in question, simulated values in relatively good agreement with measured values are obtained.