首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structures, Energetics, and Transition States of the Silicon-Phosphorus Compounds Si_2PH_n (n = 7, 5, 3, 1). An ab Initio Molecular Orbital Study
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Structures, Energetics, and Transition States of the Silicon-Phosphorus Compounds Si_2PH_n (n = 7, 5, 3, 1). An ab Initio Molecular Orbital Study

机译:硅磷化合物Si_2PH_n(n = 7、5、3、1)的结构,能级和过渡态。从头算分子轨道研究

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This study examines a variety of compounds containing silicon-phosphorus multiple bonds as well as a selection of hydrogen-bridge species, including a doubly bridged structure. The structures of 29 minima and 37 transition states of the form Si_2PH_n (n = 7, 5, 3, 1) have been optimized at the MP2(full)/6-31G(d) level of theory; a representative subset was also optimized at the QCISD/6-311G(d,p) level. Relative energies were computed using a modification of the G2 level of theory. The stability of these compounds was investigated with respect to both unimolecular rearrangement and H_2 addition/elimination. Barrier heights for 1-2 and 1-3 H-shifts and for H_2 addition/elimination span wide ranges and are dependent on the nature of the bonding. Structures that contain true silicon-phosphorus double bonds are particularly stable with respect to unimolecular rearrangement.
机译:这项研究检查了各种包含硅-磷多键的化合物以及氢桥物种的选择,包括双桥结构。 Si_2PH_n(n = 7、5、3、1)形式的29个最小值和37个过渡态的结构已在MP2(full)/ 6-31G(d)的理论水平上进行了优化;代表性子集也在QCISD / 6-311G(d,p)级别得到了优化。相对能量是通过对G2理论水平的修改来计算的。就单分子重排和H_2添加/消除而言,研究了这些化合物的稳定性。 1-2和1-3 H位移的势垒高度以及H_2添加/消除的势垒高度跨越很宽的范围,并且取决于结合的性质。含有真正的硅-磷双键的结构对于单分子重排特别稳定。

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