2023
DOI: 10.1021/acs.jpca.2c09081
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Thermal Decomposition Mechanism of Tetraethylsilane by Flash Pyrolysis Vacuum Ultraviolet Photoionization Mass Spectrometry and DFT Calculations: The Competition between β-Hydride Elimination and Bond Homolysis

Abstract: Thermal decomposition of tetraethylsilane was investigated at temperatures up to 1330 K using flash pyrolysis vacuum ultraviolet photoionization mass spectrometry. Density functional theory and transition state theory calculations were performed to corroborate the experimental observations. Both experimental and theoretical evidence showed that the pyrolysis of tetraethylsilane was initiated by Si−C bond fission to the primary reaction products, triethylsilyl (SiEt 3 ) and ethyl radicals. In the secondary reac… Show more

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Cited by 4 publications
(3 citation statements)
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“…Dimethylamino-substituted silanes also show this behavior with the rupture of the N–CH 3 bond . The Si–C bond fission was also found to be the initial reaction in flash pyrolysis of tetraethylsilane, forming ethyl radicals . To account for any changing conditions in detection throughout the experiments, the bare intensities were normalized by multiplying the intensity at a specific temperature (T) by the ratio of the intensity of the base peak ( m / z 133) at room temperature to that at the same temperature of T .…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…Dimethylamino-substituted silanes also show this behavior with the rupture of the N–CH 3 bond . The Si–C bond fission was also found to be the initial reaction in flash pyrolysis of tetraethylsilane, forming ethyl radicals . To account for any changing conditions in detection throughout the experiments, the bare intensities were normalized by multiplying the intensity at a specific temperature (T) by the ratio of the intensity of the base peak ( m / z 133) at room temperature to that at the same temperature of T .…”
Section: Resultsmentioning
confidence: 99%
“…19 The Si−C bond fission was also found to be the initial reaction in flash pyrolysis of tetraethylsilane, forming ethyl radicals. 40 To account for any changing conditions in detection throughout the experiments, the bare intensities were normalized by multiplying the intensity at a specific temperature (T) by the ratio of the intensity of the base peak (m/z 133) at room temperature to that at the same temperature of T. 37 The base peak for TMDSZ is the molecular ion peak according to Figure 1. The distribution of the normalized intensity of the CH 3 + peak as a function of filament temperature is plotted in Figure 3, which showed a fast increase in the peak intensity from 1400−2000 °C, followed by a relatively plateaued region beyond 2000 °C.…”
Section: ■ Results and Discussionmentioning
confidence: 99%
“…The dividing surfaces for the barrierless reactions at different temperatures were determined by finding the maximum Gibbs free energy change Δ G θ (T) of the “trial transition state” along the reaction pathway at individual temperatures. This computational protocol was similar to previous studies. All the rate constant calculations were performed using the KISTHELP program. ,, …”
Section: Experimental and Computational Methodsmentioning
confidence: 99%