Vibrational dynamics of the H5 + and its isotopologues from multiconfiguration time-dependent Hartree calculations

Abstract

Full-dimensional multiconfiguration time-dependent Hartree (MCTDH) computations are reported for the vibrational states of the H5 + and its H4D+, H3D2 +, H2D3 +, HD 4 +, D5 + isotopologues employing two recent analytical potential energy surfaces of Xie [J. Chem. Phys. 122, 224307 (2005)10.1063/1.1927529] and Aguado [J. Chem. Phys. 133, 024306 (2010)10.1063/1.3454658]. The potential energy operators are constructed using the n-mode representation adapted to a four-combined mode cluster expansion, including up to seven-dimensional grids, chosen adequately to take advantage in representing the MCTDH wavefunction. An error analysis is performed to quantify the convergence of the potential expansion to reproduce the reference surfaces at the energies of interest. An extensive analysis of the vibrational ground state properties of these isotopes and comparison with the reference diffusion Monte Carlo results by Acioli [J. Chem. Phys. 128, 104318 (2008)10.1063/1. 2838847] are presented. It is found that these systems are highly delocalized, interconverting between equivalent minima through rotation and internal proton transfer motions even at their vibrational ground state. Isotopic substitution affects the zero-point energy and structure, showing preference in the arrangements of the H and D within the mixed clusters, and the most stable conformers of each isotopomer are the ones with the H in the central position. Vibrational excited states are also computed and by comparing the energies and structures predicted from the two surfaces, the effect of the potential topology on them is discussed. © 2012 American Institute of Physics.