Theoretical study of the reaction of ground state atomic silicon with disilane under single collision conditions was carried out to unravel the nonadiabatic dynamics. The likely pathways on both the adiabatic triplet and singlet ground-state potential energy surfaces of Si3H6.are explored. The geometries of collision complex, intermediates, transition states, H and H2 dissociation products are optimized along with the harmonic frequencies by employing B3LYP/cc-pVTZ calculations. The energies are extrapolated to completed basis set limits, CCSD(T)/CBS. The minimum energy crossing point between triplet and singlet surfaces is located with CPMCSCF/TZVPP method. The product branching ratios were estimated with facilitation of RRKM theory. Nonadiabatic dynamics involving intersystem crossing (ISC) from the triplet to the singlet manifold, and eventually the synthesis of products via molecular hydrogen loss - is predicted. The results have compared to the findings of crossed beam experiment. The underlying chemical dynamics of the silicon – disilane reaction is quite distinct from the isovalent carbon - ethane system, which does not depict any reactivity at all, and open the door for an unconventional gas phase synthesis of hitherto elusive organosilicon molecules under single collision conditions, which cannot be synthesized by traditional preparative organometallic protocols.

Nonadiabatic dynamics of Si(3P) + Si2H6 reaction

253rd National Meeting (2017)

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