Journal of Chemical Physics, Vol.109, No.5, 1845-1859, 1998
The electronic, vibrational and rotational contributions to the dipole moment, polarizability, and first and second, hyperpolarizabilities of the BH molecule
Electronic, vibrational and rotational contributions to the dipole moment mu, polarizability alpha, and first and second hyperpolarizabilities, beta and gamma, are presented for the boron-hydride molecule; static and dynamic rovibrational properties are reported for the first time. The electronic contributions are computed ab initio :by finite differencing the electronic energy computed: at the Hartree-Fock level of theory, and using various sophisticated correlated methods. Specifically these are Moller-Plesset perturbation theory at second order, and fourth order (including single,double, triple and;quadruple substitutions), and the Brueckner variant of the coupled-cluster method including triple excitations; density functional. theory with the B3LYP functional is used for comparison. Vibrational land rotational) contributions to the properties are calculated at the Hartree-Fock level of theory; for the vibrational properties, electron correlation is partially included using second order Moller-Plesset theory. Basis set and electron correlation effects on both electronic and vibrational contributions are assessed and discussed. The dependence of the vibrational properties an, the mechanical and electrical anharmonicity is examined,,and the two methods used in its computation I;a finite difference-approach and a perturbation: theoretic method - are compared and contrasted. A brief analysis of the frequency dependence of vibrational. contributions, to alpha(-omega(sigma) ; omega(1)), beta(-omega(sigma) ; omega(1), omega(2)) in the electro-optic Pockels: and second harmonic, generation effects;, and gamma(-omega(sigma) ; omega(1) , omega(2), omega(3)) in the electro-optic Kerr and electric-field-induced : second harmonic:, generation effects, is presented. The electronic results are compared with literature values believed to the best currently available; agreement is shown to be acceptable.