A diabatic parameterization of the twofold ground state potential energy surface of the H2O-OH molecular complex

Abstract

We present a matrix functional form to fit the nearly degenerated potential energy surface of the H2O-OH molecular complex. The functional form is based on second order perturbation theory, which allows us to define two diabatic states coupled together in the field of the surrounding water molecules. The fit reproduces faithfully the fine details of the potential energy surface (PES) like the crossings and the shallow barrier between the main and secondary minima. The explicit dependence of the model on polarization ensures its transferability to systems made of several water molecules. The potential is used to investigate the structural properties of the OH radical in solution by Monte Carlo simulation. The twin surface fit shows that the second PES is shifted above the ground state by typically 1600 cm−1 for the configurations explored at a temperature of 300 K and a density of 1.0 g/cm3. The second PES has thus little influence on the structuring of water around the OH radical at such a temperature and density. Our study confirms that under these thermodynamic conditions, OH is a weak hydrogen acceptor.