Photodesorption of water from rutile(110): ab initio calculation of five-dimensional potential energy surfaces of ground and excited electronic states and wave packet studies

Abstract

In this paper, we report on our results concerning the interaction of water with titanium dioxide in its rutile modification. The (110) surface is modelled by an embedded Ti₉O₁₈Mg₇¹⁴⁺ cluster. We present up to five-dimensional potential energy surfaces for the water molecule on this surface and include the dissociation of one hydrogen atom. The electronic ground state as well as one electronically excited state is included. To deal with the multi-configurational character of the wave function, we use the complete active space self-consistent field (CASSCF) approach. The resulting potential energy surfaces are fitted by means of an artificial neural network. As a first example of quantum dynamical studies based on our potential surfaces, we present results on the photodesorption of water from rutile(110).