Dynamics of unimolecular dissociation of silylene

Ibrahim Ali , Noorbatcha and L.M., Raff and D.L, Thompson and R., Viswanathan (1986) Dynamics of unimolecular dissociation of silylene. Journal of Chemical Physics , 84 (8). pp. 4341-4346. ISSN 0021-9606

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Abstract

The semiempirical valence‐bond surface formulated by Viswanathan e t a l. [J. Phys. Chem. 8 9, 1428 (1985)] for the unimolecular dissociation of SiH2 has been fitted to an analytical function of the type suggested by Murrell and co‐workers [J. Phys. Chem. 8 8, 4887 (1984)]. The fitted surface accurately represents most of the experimental and CI results. The dynamics of the unimolecular dissociation of SiH2 to form Si and H2 have been investigated by classical trajectory methods on this fitted surface. The effect of describing the initial state of the molecule using normal and local mode approximations has been studied. In spite of the presence of the heavier atom, no bond or mode specificity is observed. The product energy distribution is found to be statistical. Using the RRK model, the high‐pressure limiting rate coefficient is found to be k(T,∞)=3.38×101 2 exp[−61.6 kcal mol− 1/RT] s− 1, which is less than the dissociation rate for SiH4. This has been attributed to the higher activation energy for SiH2 and to a statistical factor.

Item Type:	Article (Journal)
Additional Information:	3704/35143
Uncontrolled Keywords:	Physics, Atomic, Molecular & Chemical
Subjects:	Q Science > QD Chemistry
Kulliyyahs/Centres/Divisions/Institutes (Can select more than one option. Press CONTROL button):	Kulliyyah of Engineering > Department of Biotechnology Engineering
Depositing User:	Prof. Dr. Ibrahim Ali Noorbatcha
Date Deposited:	21 Feb 2014 08:52
Last Modified:	21 Feb 2014 08:52
URI:	http://irep.iium.edu.my/id/eprint/35143

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