Structures and Energetics of H6+ Clusters

Abstract

Theoretical investigations of the equilibrium structures and associated isomerization reactions of the hydrogen clusters H(6)(+) have been carried out. Three equilibrium structures and three isomerization transition states were located on the electronic doublet and quartet states of the respective potential energy surfaces. The research employed ab initio self-consistent-field (SCF), coupled cluster (CC) with single and double excitations (CCSD), CCSD with perturbative triple excitations (CCSD(T)), and full triple excitations (CCSDT) wave functions and a wide variety of correlation-consistent polarized valence cc-pVXZ and aug-cc-pVXZ (where X = D, T, Q) basis sets. For each structure the geometry, energy, dipole moment, harmonic vibrational frequencies, and infrared intensities are predicted. Complete active space SCF (CASSCF) and multireference configuration interaction (MRCI) wave functions are used to analyze the effect of correlation on physical properties and energetics. Extensive focal point analyses (including CCSDTQ and full CI energies and basis sets up to sextuple zeta) are used to obtain complete basis set (CBS) limit energies. The H(2)(+)-core H(6)(+) cluster with D(2d) symmetry is the global minimum, lying 3.9 (4.2) +/- 0.1 kcal mol(-1) below the H(3)(+)-core H(6)(+) cluster with C(s) symmetry, where zero-point vibrational energy (ZPVE) corrected value are shown in parentheses. The barrier of the isomerization reaction between these two structures is 7.4 (5.2) +/- 0.1 kcal mol(-1). The dissociation energies for the H(2)(+)-core H(6)(+) isomer [H(6)(+) (D(2d)) --> 2H(2) + H(2)(+)] and the H(3)(+)-core H(6)(+) isomer [H(6)(+) (C(s)) --> H(3)(+) + H(2) + H] are 57.5 (50.9) +/- 0.1 and 12.3 (8.3) +/- 0.1 kcal mol(-1), respectively.