Global potential energy surface and product pair-correlated distributions for the F(²P) + SiH₄ reaction – comparison with experiments

Abstract

In this paper we study the gas-phase hydrogen abstraction reaction between fluorine atoms and silane in a three-step process: potential energy surface, kinetics and dynamics. Firstly, we developed for the...

Kinetics study of the OH + SiH4 hydrogen abstraction reaction: A theoretical analysis

“…The following step in this construction was the proposition of an adequate and versatile functional form describing the whole reactive system from reactants to products. Note that the present work is the fifth of a series of reactions with silane, 16,[25][26][27] X[H, F( 2 P), Cl( 2 P), O( 3 P), OH] + SiH 4 → HX + SiH 3 , from our lab. Therefore, we took advantage of the developments with these formally similar reactions and constructed the new PES as a combination of VB/MM functionals.…”

“…In addition, it works best when only absolute minima are present, while the presence of minima and maxima makes the fitting difficult. 31 In previous works from our group, 16,26,27 we observed that when all parameters were simultaneously included in the fitting process the method was unsuccessful, our alternative being to use a step-by-step iterative process. Taking advantage of the physical meaning of the parameters in the VB/MM functional form, the process is divided in four iterative steps.…”

“…Therefore, we took advantage of the developments with these formally similar reactions and constructed the new PES as a combination of VB/MM functionals. In the previous reactions 16,25–27 the silane molecule was attacked by an atom, X, and a diatomic product, XH, was obtained, where the total potential was written as the sum of three terms, $$\begin{equation}V\; = \;{V_{{\rm{str}}}} + \;{V_{{\rm{bending}}}} + \;{V_{{\rm{op}}}}\end{equation}$$where V stret , V bending , and V op represent, respectively, the stretching, the harmonic bending, and the anharmonic out‐of‐plane motions, and depend on 34 adjustable parameters. To follow the evolution of the reaction from reactants to products, a series of switching functions are included in these terms as hyperbolic tangent functions.…”

“…Therefore, we took advantage of the developments with these formally similar reactions and constructed the new PES as a combination of VB/MM functionals. In the previous reactions 16,25–27 the silane molecule was attacked by an atom, X, and a diatomic product, XH, was obtained, where the total potential was written as the sum of three terms, $$\begin{equation}V\; = \;{V_{{\rm{str}}}} + \;{V_{{\rm{bending}}}} + \;{V_{{\rm{op}}}}\end{equation}$$…”

Theoretical study of the O(3P) + SiH4 reaction: global potential energy surface, kinetics and dynamics study

“…The title reaction represents the fourth contribution of a series of gas-phase reactions with silane, [1][2][3] X[H, F( 2 P), Cl( 2 P), O( 3 P)] + SiH 4 -HX + SiH 3 . Its theoretical study represents a theoretical challenge and is very interesting for several reasons: (i) The title reaction presents discrepancies on its mechanism of reaction.…”