A first principles polarizable water model for molecular simulations: application to a water dimer

n this paper we describe a new Hamiltonian model for polarizable water, whose reliability should in principle be independent of system dimension. Such a model is largely based on first principles using the charge density expansion and linear polarizability to treat intermolecular interactions. A semi-empirical function is added only to describe short-range atomic repulsions. The accuracy of this method has been evaluated comparing the results of our model with highly correlated quantum chemical calculations (CCSD(T)) performed on a system of two interacting water molecules. Results show that this model provides a rather accurate description of the system studied. © 2002 Elsevier Science B.V. All rights reserved.