Full-dimensional (15-dimensional) ab initio analytical potential energy surface for the H_7~+ cluster

摘要

Full-dimensional ab initio potential energy surface is constructed for the H_7~+ cluster. The surface is a fit to roughly 160 000 interaction energies obtained with second-order M?llerPlesset perturbation theory and the cc-pVQZ basis set, using the invariant polynomial method [B. J. Braams and J. M. Bowman, Int. Rev. Phys. Chem. 28, 577 (2009)]. We employ permutationally invariant basis functions in Morse-type variables for all the internuclear distances to incorporate permutational symmetry with respect to interchange of H atoms into the representation of the surface.We describe how different configurations are selected in order to create the database of the interaction energies for the linear least squares fitting procedure. The root-mean-square error of the fit is 170 cm~(?1_ for the entire data set. The surface dissociates correctly to the H_5+~ + H_2 fragments. A detailed analysis of its topology, as well as comparison with additional ab initio calculations, including harmonic frequencies, verify the quality and accuracy of the parameterized potential. This is the first attempt to present an analytical representation of the 15-dimensional surface of the H_7~+ cluster for carrying out ynamics studies.