Heats of formation of chlorosilanes (SiHmCln) calculated by ab initio molecular orbital methods

Su, Ming Der; Schlegel, H. Bernhard

doi:10.1021/j100136a014

Cited by 56 publications

(55 citation statements)

References 5 publications

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“…With this one exception, however, the mechanism presented here appears to reconcile the various experimental observations on dichlorosilane decomposition with the predictions of the ab initio calculations. 14,15 …”

Section: Comparison With Experimental Observationsmentioning

confidence: 99%

See 1 more Smart Citation

On the Mechanism of Homogeneous Decomposition of the Chlorinated Silanes. Chain Reactions Propagated by Divalent Silicon Species

Swihart

Carr

1998

J. Phys. Chem. A

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A mechanism for the homogeneous gas-phase decomposition of SiHCl 3 , SiH 2 Cl 2 , and SiH 3 Cl in hydrogen is derived from the results of ab initio molecular-orbital studies. It consists of 39 reversible elementary reactions among 25 species, including pressure-dependent unimolecular decomposition of the chlorinated silanes and secondary chemistry due to reactions of SiH 2 , SiHCl, and SiCl 2 with one another and with the chlorinated silanes. Rate parameters in the mechanism have been calculated based on results of ab initio studies using transition-state theory and unimolecular rate theories. This allows us to construct a reasonably complete mechanism that provides qualitative explanations for several features of dichlorosilane decomposition that have been presented in the literature, including observations on the presence and concentrations of SiCl 2 , SiHCl, and Si atoms. Several chain reactions in which the chain carriers are divalent silicon species have been identified.

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Section: Comparison With Experimental Observationsmentioning

confidence: 99%

“…CVD reactor models that included reactions in the gas phase 14,15 have assumed that the reaction was SiH 2 Cl 2 f SiCl 2 + H 2 . These models also used rate parameters that gave reaction rates that were orders of magnitude larger than the rates of the unimolecular decomposition reactions predicted from the ab initio calculations.…”

Section: Introductionmentioning

confidence: 99%

On the Mechanism of Homogeneous Decomposition of the Chlorinated Silanes. Chain Reactions Propagated by Divalent Silicon Species

Swihart

Carr

1998

J. Phys. Chem. A

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“…The value adopted by JANAF [17] is rejected by many workers [18,19]. In the present case we are using the data proposed by Su and Schlegel [20].…”

Section: H Atom Aras Measurementsmentioning

confidence: 99%

Kinetics of the initiation step of the thermal decomposition of SiCl4

Catoire

Woiki²,

Roth

1997

Int. J. Chem. Kinet.

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The initiation reaction of the thermal decomposition of silicon tetrachloride (R1) was studied behind reflected shock waves at temperatures between 1550 K and 2370 K and pressures between 1 and 1.5 bar. Atomic resonance absorption spectrometry (ARAS) was applied for time-resolved measurements of H atoms at the L ␣ -line in SiCl 4 /H 2 /Ar systems. Additional experiments were performed in the SiCl 4 /Ar system following the absorption of SiCl 4 at the L ␣ -line. Rate coefficients for the reaction (R1) were determined to be:The choice between two possible alternatives of the first decomposition step, namely elimination of either Cl 2 or Cl, has been made in favor of the second reaction on the basis of kinetic and energetic considerations.

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“…Nevertheless, it is to be noted that there is a considerable disagreement in the literature over the value for SiCl 3 formation enthalpy. The recent value calculated by Su and Schlegel [11] was used to calculate the reaction enthalpy of (R1). A comparison of k 1 with literature values is not possible because there are no data available.…”

mentioning

confidence: 99%

A shock tube study of the reaction of H atoms with SiCl4

Catoire¹,

Woiki²,

Roth³

1997

Int. J. Chem. Kinet.

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ABSTRACT:The reaction of H atoms with SiCl 4 was studied behind reflected shock waves at temperatures between 1530 K and 1730 K and pressures around 1.5 bar by applying atomic resonance absorption spectroscopy (ARAS) for time resolved measurements of H atoms at the L ␣ -line. The thermal decomposition of a few ppm ethyl iodide (C 2 H 5 I) was used as a Hatom source. In the presence of a high excess of the molecular reactant SiCl 4 a slow consumption of H was observed, which follows a pseudo-first-order rate law. Rate coefficient for the consumption of H by the reaction: (R1) was determined to be:.

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Heats of formation of chlorosilanes (SiHmCln) calculated by ab initio molecular orbital methods

Cited by 56 publications

References 5 publications

On the Mechanism of Homogeneous Decomposition of the Chlorinated Silanes. Chain Reactions Propagated by Divalent Silicon Species

On the Mechanism of Homogeneous Decomposition of the Chlorinated Silanes. Chain Reactions Propagated by Divalent Silicon Species

Kinetics of the initiation step of the thermal decomposition of SiCl4

A shock tube study of the reaction of H atoms with SiCl4

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