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J Chem Phys. 2004 Sep 22;121(12):5777-82.

Ab initio study of the reactions of Ga((2)P, (2)S, and (2)P) with silane.

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Area de Física Atómica y Molecular Aplicada, CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Avenida San Pablo 180, Col. Reynosa Tamaulipas, México 02200, Distrito Federal, Mexico.


The interactions of Ga((2)P:4s(2)4p(1), (2)S:4s(2)5s(1), and (2)P:4s(2)5p(1)) with SiH(4) are studied by means of Hartree-Fock self-consistent field (SCF) and multiconfigurational SCF followed by extensive variational and perturbational second-order multireference Møller-Plesset configuration by perturbation selected by iterative process calculations, using relativistic effective core potentials. The Ga atom in its (2)P(4s(2)5p(1)) state can spontaneously insert into the SiH(4). The Ga atom in its (2)S(4s(2)5s(1)) state is inserted into the SiH(4). In this interaction the 3 (2)A(') potential energy surface initially attractive becomes repulsive after meeting the 2 (2)A(') surface linked with the Ga((2)P:4s(2)4p(1))+SiH(4) fragments. The two (2)A(') curves (2 (2)A(') and X (2)A(')) derived from the interaction of Ga((2)P:4s(2)4p(1)) atom with silane molecule are initially repulsive. The 2 (2)A(') curve after an avoided crossing with the 3 (2)A(') curve goes down until it meets the X (2)A(') curve. The 2 (2)A(') curve becomes repulsive after the avoided crossing with the X (2)A(') curve. The X (2)A(') curve becomes attractive only after its avoided crossing with the 2 (2)A(') curve. The lowest-lying X (2)A(') potential leads to the HGaSiH(3)X (2)A(') intermediate molecule. This intermediate molecule, diabatically correlated with the Ga((2)S:4s(2)5s(1))+SiH(4) fragments, which lies 1.5 kcal/mol above the ground state reactants leads to the GaH+SiH(3) or H+GaSiH(3) products through the dissociation channels. These products are reached from the HGaSiH(3) intermediate without activation barriers. This work shows that the Ga atom at its first excited state in the presence of silane molecules in gas phase leads to the formation of SiH(3) radicals, H atoms, GaH hydrides, as well as gallium silicide molecules.

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