Full-dimensional (15-dimensional) ab initio analytical potential energy surface for the H7+ cluster.
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 MöllerPlesset 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 dynamics studies.
Instituto de Física Fundamental, CSIC, Serrano 123, 28006 Madrid, Spain.
Patricia
P
Barragán
Rita
R
Prosmiti
Yimin
Y
Wang
Joel M
JM
Bowman