The GaOH–HGaO potential energy hypersurface and the necessity of correlating the 3d electrons

Abstract

The ground state potential energy hypersurface of the GaOH–HGaO system has been investigated using high level ab initio molecular electronic structure theory. The geometries and physical properties of two equilibrium structures, one isomerization transition state and one inversion transition state were determined at the self-consistent field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double excitations (CCSD), and CCSD with perturbative triple excitations [CCSD(T)] levels of theory with four sets of basis functions. It has been found that freezing the 3d electrons of the Ga atom in the correlation procedures is not appropriate for this system. For the energy difference ΔE (GaOH–HGaO) the freezing of the 3d electrons results in an error of 25 kcal/mol! The dipole moments, harmonic vibrational frequencies, and infrared (IR) intensities are predicted for the four stationary points. At the highest level of theory employed in this study, CCSD(T) using triple zeta plus double polarization with higher angular momentum and diffuse functions [TZ2P(f,d)+diff] basis set, the bent GaOH was found to be 41.9 kcal/mol more stable than the linear HGaO species; with the zero-point vibrational energy (ZPVE) correction, the energy separation becomes 40.4 kcal/mol. The classical barrier height for the exothermic isomerization (1,2 hydrogen shift) reaction HGaO→GaOH is determined to be 44.5 kcal/mol and the barrier height with the ZPVE correction 42.3 kcal/mol. The classical barrier to linearity for the bent GaOH molecule is determined to be 1.7 kcal/mol and the barrier height with the ZPVE correction to be 1.2 kcal/mol. The predicted dipole moments of GaOH and HGaO are 1.41 and 4.45 Debye, respectively. The effects of electron correlation reduce the dipole moment of HGaO by the sizable amount of 1.2 Debye. The two equilibrium species may be suitable for microwave spectroscopic investigation. Furthermore, they may also be detectable by IR techniques due to the relatively large intensities of their vibrational modes. The geometrical and energetic features are compared with those of the valence isoelectronic HXO–XOH systems, where X is a group IIIA atom and the HXO+–XOH+ systems, where X is a group IVA atom.