Construction of exchange repulsion in terms of the wave functions at QM/MM boundary region.

We developed a simple method to calculate exchange repulsion between a quantum mechanical (QM) solute and a molecular mechanical (MM) molecule in the QM/MM approach. In our method, the size parameter in the Buckingham type potential for the QM solute is directly determined in terms of the one-electron wave functions of the solute. The point of the method lies in the introduction of the exchange core function (ECF) defined as a Slater function which mimics the behavior of the exterior electron density at the QM/MM boundary region. In the present paper, the ECF was constructed in terms of the Becke-Roussel (BR) exchange hole function. It was demonstrated that the ECF yielded by the BR procedure can faithfully reproduce the radial behavior of the electron density of a QM solute. The size parameter of the solute as well as the exchange repulsion are, then, obtained using the overlap model without any fitting procedure. To examine the efficiency of the method, it was applied to calculation of the exchange repulsions for minimal QM/MM systems, hydrogen-bonded water dimer, and H3O(+)-H2O. We found that our approach is able to reproduce the potential energy curves for these systems showing reasonable agreements with those given by accurate full quantum chemical calculations.