Transition probabilities for the Au (2S, 2D, and 2P) with SiH4 reaction

Transition probabilities on the interaction of the ground and the lowest excited states of gold Au (S-2:5d(10)6s(1), D-2:5d(9)6s(2), and P-2:5d(10)6p(1)) with silane (SiH4) are studied through ab initio Hartree-Fock self-consistent field calculations, where the atom's core is represented by relativistic effective core potentials. These calculations are followed by a multiconfigurational self-consistent field study. The correlation energy is accounted for through extensive variational and perturbative second order multireference Moller-Plesset configuration interaction analysis of selected perturbations obtained by iterative process calculations using the CIPSI program package. It is found that the Au atom in the (P-2:5d(10)6p(1)) state inserts in the Si-H bond. In this interaction its corresponding D (2)A(') potential energy surface is initially attractive and only becomes repulsive after encountering an avoided crossing with the initially repulsive C (2)A(') surface linked to the Au(D-2:5d(9)6s(2))-SiH4 fragments. The A, B, and C (2)A(') curves derived from the Au(D-2:5d(9)6s(2)) atom interaction with silane are initially repulsive, each one of them showing two avoided crossings, while the A (2)A(') curve goes sharply downwards until it meets the X (2)A(') curve interacting adiabatically, which is linked with the Au(S-2:5d(10)6s(1))-SiH4 moieties. The A (2)A(') curve becomes repulsive after the avoided crossing with the X (2)A('), curve. The lowest-lying X (2)A(') potential leads to the HAuSiH3 X (2)A(') intermediate molecule. This intermediate molecule, diabatically correlated with the Au(P-2:5d(10)6p(1))+SiH4 system which lies 3.34 kcal/mol above the ground state reactants, has been carefully characterized as have the dissociation channels leading to the AuH+SiH3 and H+AuSiH3 products. These products are reached from the HAuSiH3 intermediate without any activation barrier. The Au-SiH4 calculation results are successfully compared to experiment. Landau-Zener theory of avoided crossings is applied to these interactions considering the angle theta instead of the distance r as the reaction coordinate.