Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849-5312, USA.
J Phys Chem A. 2011 Aug 4;115(30):8532-9. doi: 10.1021/jp2036247. Epub 2011 Jul 11.
The CBS-QB3 and G4 thermochemical models have been used to generate energetic, structural, and spectroscopic data on a set of molecules with trivalent or pentavalent phosphorus atoms that can serve as simulants of chemical warfare agents. Based on structural data, the conformational stabilities of these molecules are explained in terms of the anomeric interaction within the OPOC and OPSC fragments. For those cases where experimental data are available, comparisons have been made between calculated and previously reported vibrational frequencies. All varieties of bond dissociation energies have been examined except those for C-H and P═O bonds. In trivalent phosphorus molecules, the O-C and S-C bonds have the lowest dissociation energies. In the pentavalent phosphorus set, the S-C bonds, followed by P-S bonds, have the lowest dissociation energies. In the fluorinated simulant molecules, the P-F bond is strongest, and the P-C or O-C bonds are weakest.
CBS-QB3 和 G4 热化学模型已被用于生成一组具有三价或五价磷原子的分子的能量、结构和光谱数据，这些分子可用作化学战剂的模拟物。基于结构数据，用 OPOC 和 OPSC 片段内的端基相互作用解释了这些分子的构象稳定性。对于有实验数据的情况，将计算值与之前报道的振动频率进行了比较。除了 C-H 和 P═O 键之外，所有种类的键离解能都进行了研究。在三价磷分子中，O-C 和 S-C 键具有最低的离解能。在五价磷组中，S-C 键，其次是 P-S 键，具有最低的离解能。在氟化模拟物分子中，P-F 键最强，而 P-C 或 O-C 键最弱。
