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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Homogeneous decomposition mechanisms of diethylzine by Raman spectroscopy and quantum chemical calculations
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Homogeneous decomposition mechanisms of diethylzine by Raman spectroscopy and quantum chemical calculations

机译：拉曼光谱和量子化学计算的二乙嗪均相分解机理

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摘要

The gas-phase decomposition pathways of diethylzinc (DEZn), a common precursor for deposition of Zn-VI compounds, were investigated in detail. The homogeneous thermal decomposition of DEZn in N-2 carrier was followed in an impinging-jet, up-flow reactor by Raman scattering. Density Functional Theory calculations were performed to describe the bond dissociation behavior using the model chemistry B3LYP/6-311G(d) to estimate optimal geometries and Raman active vibrational frequencies of DEZn, as well as anticipated intermediates and products. Comparison of the measured DEZn decomposition profile to that predicted by a 2-D hydrodynamic simulation revealed that simple bond dissociation between zinc and carbon atoms is the dominant homogeneous thermal decomposition pathway. The calculations suggest several reactions involving intermediates and Raman scattering experiments confirming the formation of the dimer (ZnC2H5)(2), In a different set of experiments, photolysis of DEZn gave evidence for decomposition by beta-hydride elimination. The results suggest that beta-hydride elimination is a minor pathway for the gas-phase homogeneous pyrolysis of diethylzinc. A reasonable transition state during beta-hydride elimination was identified, and the calculated energies and thermodynamic properties support the likelihood of these reaction steps.
机译：详细研究了二乙基锌（DEZn）的气相分解途径，二乙基锌是沉积Zn-VI化合物的常见前体。在N-2载流子中DEZn的均匀热分解，随后通过拉曼散射在冲击射流上流反应器中进行。进行了密度泛函理论计算，以描述化学模型B3LYP / 6-311G（d）的键解离行为，以估计DEZn的最佳几何形状和拉曼活性振动频率，以及预期的中间体和产物。将测得的DEZn分解曲线与2-D流体动力学模拟预测的曲线进行比较，发现锌和碳原子之间的简单键解离是主要的均相热分解途径。计算结果表明，涉及中间体和拉曼散射实验的数个反应证实了二聚体（ZnC2H5）（2）的形成。在另一组实验中，DEZn的光解作用为β-氢化物消除提供了分解证据。结果表明，β-氢化物消除是二乙基锌气相均相热解的次要途径。确定了消除β-氢化物期间的合理过渡态，并且计算出的能量和热力学性质支持了这些反应步骤的可能性。

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