An evaluation of the kinetic data for hydrogen abstraction from silanes in the gas phase

Arthur, N. L.; Bell, T. N.

doi:10.1007/bf03055540

Cited by 78 publications

(39 citation statements)

References 96 publications

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“…The rate constants of the two channels, k 1a , and k 2a , are evaluated by conventional transition state theory Figure 4 and given in Table 4 along with the available experimental results. [1][2][3][4][5] The calculated rate constant value of k 1a is in good agreement with the available experimental value. [1,[3][4][5] …”

Section: Rate Constantssupporting

confidence: 86%

“…at 350 K. In 1973 and 1978, kinetic data were also evaluated by two groups, Berkley [4] and Arthur, [5] for the reaction Because measurements were done mostly at the lower temperature range of practical interest and no experimental information is available on the higher temperature of the title reaction, theoretical investigation is desirable to give a further understanding of the mechanism of this multiple channel reaction and to evaluate the rate constant at high temperatures. To the best of our knowledge, no previous theoretical work has been performed on the kinetics of the title reactions.…”

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confidence: 99%

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Theoretical study on the reaction CX₃ + SiH(CH₃)₃ (X = H, F)

Zhang

Liu

et al. 2011

J Comput Chem

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Theoretical investigations are carried out on the multiple-channel reactions, CH(3) + SiH(CH(3))(3) → products and CF(3) + SiH(CH(3))(3) → products. The minimum energy paths (MEP) are calculated at the MP2/6-311 + G(d,p) level, and energetic information is further refined by the MC-QCISD (single point) method. The rate constants for major reaction channels are calculated by the canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 200-1500 K. The theoretical rate constants are in good agreement with the available experimental data and are found to be k(1a)(T) = 1.93 × 10(-24) T(3.15) exp(-1214.59/T) and k(2a)(T) = 1.33 × 10(-25) T(4.13) exp(-397.94/T) (in unit of cm(3) molecule(-1) s(-1)). Our calculations indicate that hydrogen abstraction channel from SiH group is the major channel due to the smaller barrier height among five channels considered.

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Section: Rate Constantssupporting

confidence: 86%

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confidence: 99%

Theoretical study on the reaction CX₃ + SiH(CH₃)₃ (X = H, F)

Zhang

Liu

et al. 2011

J Comput Chem

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“…Accordingly, the scatter of the reported rate constants is large especially for the systems H/SiH 4 and H/CH 3 SiH 3 [1],…”

Section: Introductionmentioning

confidence: 99%

“…The reactions of hydrogen atoms with silane and the methylsilanes have been the subject of a number of studies [1], There exists agreement that the primary step comprises a simple abstraction reaction (1) H + R 3 SiHH 2 + R 3 Si.…”

Section: Introductionmentioning

confidence: 99%

The Reaction of Hydrogen Atoms with Silyl Radicals; the Decomposition Pathways of Chemically Activated Silanes

Reimann

Potzinger

1983

Zeitschrift Für Naturforschung A

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The reactions of hydrogen atoms with silane and the methylated silanes -with the exception of tetramethylsilane -have been investigated in a fast flow reactor. Under our experimental conditions hydrogen abstraction from the Si-H bond is followed by combination of hydrogen atoms with the corresponding silyl radicals. The molecules formed in this way are activated by about 375 kJ/mol of vibrational energy. Two decomposition channels have been unequivocally identified, namely the elimination of molecular hydrogen and of methane, both with concomittant formation of the respective silylenes. In a subsequent step, silylene inserts into the substrate under formation of disilanes. With increasing degree of methylation. stabilization of the activated molecule competes with decomposition and dominates the kinetics in the case of trimethylsilane. With methyl-and dimethyl-silane, methyl radicals are observed as an additional reaction product. On the basis of RRKM calculations it is unlikely that they originate from a direct decomposition of the activated molecules.Absolute values for the room temperature rate constants of the abstraction reactions are given; for H + CH 3 SiH 3 , Arrhenius parameters have been determined.

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“…Figure 6c presents our RD SCTST rate constants in comparison with experimental results. [71][72] Rate constants for R3 are presented in Table 7. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 24 ________________________________________________________________________ For reactions with small skew angles and large reaction path curvature such as R3, corner-cutting effects have been shown to be important.…”

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confidence: 99%

Reduced-Dimensionality Semiclassical Transition State Theory: Application to Hydrogen Atom Abstraction and Exchange Reactions of Hydrocarbons

2015

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Quantum mechanical methods for calculating rate constants are often intractable for reactions involving many atoms. Semiclassical transition state theory (SCTST) offers computational advantages over these methods but nonetheless scales exponentially with the number of degrees of freedom (DOFs) of the system. Here we present a method with more favorable scaling, reduced-dimensionality SCTST (RD SCTST), that treats only a subset of DOFs of the system explicitly. We apply it to three H abstraction and exchange reactions for which two-dimensional potential energy surfaces (PESs) have previously been constructed and evaluated using RD quantum scattering calculations. We differentiated these PESs to calculate harmonic frequencies and anharmonic constants, which were then used to calculate cumulative reaction probabilities and rate constants by RD SCTST. This method yielded rate constants in good agreement with quantum scattering results. Notably, it performed well for a heavy-light-heavy reaction, even though it does not explicitly account for corner-cutting effects. Recent extensions to SCTST that improve its treatment of deep tunneling were also evaluated within the reduced-dimensionality framework. The success of RD SCTST in this study suggests its potential applicability to larger systems.

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An evaluation of the kinetic data for hydrogen abstraction from silanes in the gas phase

Cited by 78 publications

References 96 publications

Theoretical study on the reaction CX₃ + SiH(CH₃)₃ (X = H, F)

Theoretical study on the reaction CX₃ + SiH(CH₃)₃ (X = H, F)

The Reaction of Hydrogen Atoms with Silyl Radicals; the Decomposition Pathways of Chemically Activated Silanes

Reduced-Dimensionality Semiclassical Transition State Theory: Application to Hydrogen Atom Abstraction and Exchange Reactions of Hydrocarbons

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An evaluation of the kinetic data for hydrogen abstraction from silanes in the gas phase

Cited by 78 publications

References 96 publications

Theoretical study on the reaction CX3 + SiH(CH3)3 (X = H, F)

Theoretical study on the reaction CX3 + SiH(CH3)3 (X = H, F)

The Reaction of Hydrogen Atoms with Silyl Radicals; the Decomposition Pathways of Chemically Activated Silanes

Reduced-Dimensionality Semiclassical Transition State Theory: Application to Hydrogen Atom Abstraction and Exchange Reactions of Hydrocarbons

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Theoretical study on the reaction CX₃ + SiH(CH₃)₃ (X = H, F)

Theoretical study on the reaction CX₃ + SiH(CH₃)₃ (X = H, F)