RESUMO
A polarizable version of the rigid seven-site (TIP7P) water model with the atom-bond electronegativity equalization method (ABEEM) is proposed. The model uses direct polarization, where an isolated water monomer in the equilibrium geometry is assumed as a reference state and the polarization of the monomer arises from interacting with other molecules as a perturbation of the reference state. The charge on each site of the monomer splits into reference charge and perturbation charge. The perturbation charge arises only because of other reference charges. The interaction of the perturbation charge with other perturbation charges is replaced using polarization scaling to enhance the interaction of perturbation charge with the reference charges of the sites from other molecules. The perturbation charges are updated by evaluating explicit expressions once. This direct polarization is time-reversible because the charge update is independent of the charges in previous simulation steps. A Slater-type damping function moderates the short-range electrostatics to treat charge diffusion. The Ewald method corrects the long-range electrostatics both in the nuclei movement and in electronegativity equalization to diminish the size effect. The water model is parameterized by fitting the ab initio results of water clusters and the experimental results of water monomers and thermodynamic properties for liquid water. Owing to polarizability, the model performs better than the TIP7P model in terms of vaporization enthalpy, isothermal compressibility, and shear viscosity of the liquid phase. It performs better at the melting point of ice but slightly worse under critical conditions than the TIP7P model. Direct polarization has a low time complexity of O(N) and is a good choice for ABEEM to improve its computational efficiency.
RESUMO
Constant pressure simulations were carried out to construct a new rigid nonpolarizable seven-site water model (TIP7P), which is an effective and efficient version of flexible seven-fluctuating-charge water model. In this model, the positive charges are located on three nuclei and the negative charges disperse on two bond sites at the geometric center of each OH bond and two lone-pair sites along the tetrahedral direction away from the oxygen atom. Our new model performs better than other models in properties, such as radial distribution function, liquid density, thermal expansion coefficient, isothermal compressibility, vaporization enthalpy, isobaric heat capacity, static dielectric constant, self-diffusion coefficient, critical temperature, and density. This model reproduces liquid density and static dielectric constant over the temperatures from 253 to 373 K at 1 atm with the standard deviation of 0.0010 g/cm3 and 1.37 to the experimental data, respectively. The maximum density is 1.0006 g/cm3 at 277 K. The calculated isobaric compressibility presents a minimum at about 310 K close to the experimental value of 319 K. The self-diffusion coefficient agrees the experimental data with the standard deviation of 0.55 × 10-5 cm2/s, although it is not the target property for parameterization. Liquid-vapor phase equilibrium was examined in slab simulations. The evaluated critical temperature and density are 633 K and 0.337 g/cm3 close to the experimental values of 647.096 K and 0.322 g/cm3. This model also presents reasonable vaporization enthalpy and isobaric heat capacity. Based upon good performances mentioned, our new model is a good choice for more accurate investigation to large molecular systems.
