A linear-scaling self-consistent generalization of the multistate empirical valence bond method for multiple excess protons in aqueous systems

An extension to the multistate empirical valence bond (MS-EVB) method is presented in this paper that is capable of treating multiple excess protons within the context of molecular-dynamics simulation. The computational cost of the method scales linearly with respect to the number of excess protons. Calculations for a 0.44 M HCl systems are carried out to illustrate the multiproton extension of the MS-EVB method. A significant decrease in the Eigen-type H9O4+ cation is observed in the contact ion-pair configuration formed between Cl- and hydronium ions. (C) 2005 American Institute of Physics.