Ab Initio and Electron Propagator Theory Study of Boron Hydrides

Abstract

Boron hydrides (BH3, B2H6, B3H7, B4H10, B5H9, and B5H11) and their cations are studied by the coupled cluster CCSD(T) theory, the second-order Mller-Plesset (MP2) perturbation method, and the electron propagator theory in the partial third-order quasi-particle approximation, using the 6-311G(d,p) basis set. The vertical ionization potential energies are calculated, indicating an excellent agreement with the experimental data from photoelectron spectroscopy. Assignments to the experimental spectra are made on the basis of the present computational analyses. A significant Jahn-Teller effect on BH3+ leads to two states, 2A1 and 2B2, with the split energy of 0.14 eV. The triple and double B-H-B bridges are formed in B2H6+ and b-B3H7+, respectively. A new B-H-B bridge is formed while two B-B bonds are broken in B5H11+. The Jahn-Teller effect lowers the symmetry of B5H9 (C4v) to B5H9+ (C2) but slightly influences the structure of ara-B4H10 (C2v). The calculated properties of geometries, vibrational frequencies, and energies are compared with the experimental data available in the literatures.