Kinetics of the initiation step of the thermal decomposition of SiCl4

Catoire, L.; Woiki, D.; Roth, P.

doi:10.1002/(sici)1097-4601(1997)29:6<415::aid-kin2>3.0.co;2-x

Cited by 18 publications

(20 citation statements)

References 15 publications

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“…In both studies, the high pressure limit rate constants were derived from VTST calculations as the reaction proceeds barrierless towards the resulted in final rate constants that are in close agreement with each other. These theoretical rate constants are compared in Figure 9 to the experimental values of Catoire et al 30 and Kunz and Roth 4 . It appears, from the discrepancy between the theoretical high pressure limits and the experimental values of Catoire et al, that reaction R2 must exhibit a significant pressure dependence, especially at high temperature, as suggested by the increase of the ratio k∞/kexp.…”

Section: Reaction Sicl4 + H (R1 and R5)mentioning

confidence: 96%

Theoretical Reassessment and Model Validation of Some Kinetic Parameters Relevant to Si/Cl/H Systems

Diévart

Catoire

2021

J. Phys. Chem. A

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The increasing demand in silicon based materials requires the optimization of silicon deposit manufacturing processes and therefore a better understanding of the gas-phase reactivity of silicon precursors such as silicon tetrachloride (SiCl4). In the present work, hydrogen atoms resonance absorption spectroscopy (H-ARAS) have been used to investigate the high temperature reactivity of SiCl4 behind reflected shock waves at ~1.5 atm in the presence of either ethyl iodide or molecular hydrogen, used as H atoms precursors. Several key reactions of SiCl4 and its main gas-phase decomposition products (SiCl3, Cl, SiHCl3, SiHCl2) have been determined theoretically. The structures and vibrational frequencies of reactants, products, and tight transition states were determined at the B2PLYP-D3/aug-cc-pVTZ level, and final single point energies refined from extrapolated RCCSD(T)/aug-cc-pVnZ (n = D, T, and Q) calculations. The minimum-energy paths of barrierless reactions were calculated at the NEVPT2 level. Final rate constants were then derived from Transition State Theory (TST) and Variational TST/Master Equation analysis within the rigid rotor harmonic oscillations framework. A kinetic mechanism was assembled, based on the present ab initio calculations, to successfully model and interpret the experimental absorption profiles. Sensitivity analysis unambiguously highlighted the need to account for the pressure dependence in the SiCl4 decomposition (SiCl4 ⇄ SiCl3 + Cl), while discarding previous theoretical and experimental determinations of this rate constant.

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Section: Reaction Sicl4 + H (R1 and R5)mentioning

confidence: 96%

Theoretical Reassessment and Model Validation of Some Kinetic Parameters Relevant to Si/Cl/H Systems

Diévart

Catoire

2021

J. Phys. Chem. A

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“…The reactions involving gaseous are well known to be SiCl 4 important in the chemical vapor deposition processes used for the synthesis of SiC and Ðlms.1h3 Knowledge of the Si 3 N 4 kinetic properties of these reactions is necessary for the further development of these gas phase processes. Experimentally, Catoire et al 4…”

Section: Introductionmentioning

confidence: 99%

Ab initio study on the rate constants of SiCl4 + H→SiCl3 + HCl

Zhang¹,

Ye²,

Li³

et al. 2001

Phys. Chem. Chem. Phys.

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The reaction is studied using an ab initio dynamic method. The direct chlorine SiCl 4 ] H ] SiCl 3 ] HCl abstraction of reaction processes via a symmetry transition state is calculated by the intrinsic reaction C 3v coordinate (IRC) method at the UMP2/6-311G(d,p) level. The forward and reverse barriers are reÐned by UMP4(SDTQ) and UQCISD(T) single point energy calculations using the same basis set of 6-311G(d,p). The forward barrier is calculated to be 24.34 kcal mol~1 at the UMP4(SDTQ) level and 22.62 kcal mol~1 at the UQCISD(T) level, while the reverse barrier is 22.46 and 21.90 kcal mol~1, respectively. The enthalpy of reaction is calculated to be 1.94 kcal mol~1 at the UMP4(SDTQ) level and 0.72 kcal mol~1 at the UQCISD(T) level. The forward rate constants in the temperature range 1500È1800 K are calculated by the conventional and variational transition state theory (CVT) with small-curvature tunneling (SCT) correction. The variational e †ect is important for the calculation of forward rate constants but the SCT correction is small. The CVT and CVT/SCT rate constants of the forward reaction at the UMP4(SDTQ) and UQCISD(T) levels are consistent with the lower limit of the experimental result. However, the theoretical activation energies in the temperature range 1500È1800 K, 28.43 kcal mol~1 at the UMP4(SDTQ) level and 27.10 kcal mol~1 at the UQCISD(T) level, are much higher than the experimental value, 9.54 ^5.17 kcal mol~1. The theoretical temperature dependence of the rate constants di †ers from the experimental result.

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“…The error bars shown in the figures represent one standard deviation based on several data runs. 34 ' 35 and Powers,' 4 respectively. These papers suggested that the initial steps produce the radical SiCI 3 rather than SiCI 2 .…”

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confidence: 99%