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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical study on structures and stability of Si2CP isomers
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Theoretical study on structures and stability of Si2CP isomers

机译：Si2CP异构体的结构和稳定性的理论研究

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The structures, energetics, spectroscopies, and isomerization of various doublet Si2CP species are explored theoretically. In contrast to the previously studied SiC2N and SiC2P radicals that have linear SiCCN and SiCCP ground states, the title Si2CP radical has a four-membered-ring form cSiSiPC 1 (0.0 kcal/mol) with Si-C cross-bonding as the ground-state isomer at the CCSD(T)/6-311G(2df)//B3LYP/6-311G(d)+ZPVE level, similar to the Si2CN radical. The second low-lying isomer 2 at 11.6 kcal/mol has a SiCSiP four-membered ring with C-P cross-bonding, yet it is kinetically quite unstable toward conversion to 1 with a barrier of 3.5 kcal/mol. In addition, three cyclic species with divalent carbene character, i.e., cSiSiCP 7, 7' with C-P cross-bonding and cSiCSiP 8 with Si-Si cross-bonding, are found to possess considerable kinetic stability, although they are energetically high lying at 44.4, 46.5, and 41.4 kcal/mol, respectively. Moreover, a linear isomer SiCSiP 5 at 44.3 kcal/mol also has considerable kinetic stability and predominantly features the interesting cumulenic vertical bar Si=C Si=P vertical bar center dot form with a slight contribution from the silicon-phosphorus triply bonded form vertical bar Si=C center dot-Si equivalent to P vertical bar. The silicon-carbon triply bonded form center dot Si equivalent to C-Si equivalent to P vertical bar has negligible contribution. All five isomers are expected to be observable in low-temperature environments. Their bonding nature and possible formation strategies are discussed. For relevant species the QCISD/6-311G(d) and CCSD(T)/6-311+G(2df) (single-point) calculations are performed to provide more reliable results. The calculated results are compared to those of the analogous C3N, C3P, SiC2N, and Si2CN radicals with 17 valence electrons. Implications in interstellar space and P-doped SiC vaporization processes are also discussed.
机译：从理论上探讨了各种双峰Si2CP物种的结构，能级，光谱学和异构化。与先前研究的具有线性SiCCN和SiCCP基态的SiC2N和SiC2P自由基相反，标题Si2CP自由基具有四元环形式的cSiSiPC 1（0.0 kcal / mol），且Si-C交叉键为基态。 CCSD（T）/ 6-311G（2df）// B3LYP / 6-311G（d）+ ZPVE能级的三态同分异构体，类似于Si2CN基团。第二个低洼异构体2为11.6 kcal / mol，具有SiCSiP四元环，具有C-P交叉键，但在转化为1时，动力学上非常不稳定，势垒为3.5 kcal / mol。此外，发现具有二价卡宾特性的三个环状物质，即具有CP交叉键的cSiSiCP 7、7'和具有Si-Si交叉键的cSiCSiP 8，尽管在能量上较高，为44.4，但具有相当大的动力学稳定性。 ，分别为46.5和41.4 kcal / mol。此外，线性异构体SiCSiP 5在44.3 kcal / mol时也具有相当大的动力学稳定性，并且主要具有有趣的积云垂直条Si = C Si = P垂直条中心点形式，而硅-磷三键结合的垂直条略有贡献Si = C中心点-Si等效于P竖线。硅碳三键结合形成的中心点Si等效于C-Si等效于P竖线，其贡献可忽略不计。预计所有五个异构体在低温环境下均可观察到。讨论了它们的键合性质和可能的形成策略。对于相关物种，执行QCISD / 6-311G（d）和CCSD（T）/ 6-311 + G（2df）（单点）计算以提供更可靠的结果。将计算结果与具有17个价电子的类似C3N，C3P，SiC2N和Si2CN自由基的结果进行比较。还讨论了星际空间和P掺杂SiC汽化过程的含义。

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