HFSiS构型及其稳定性的理论研究

利用密度泛函理论对三线态HFSiS分子结构及其稳定性进行了详细的理论研究.在B3LYP/6-311G**水平上计算出了各驻点的优化构型、振动频率,并对各个振动模式加以归属,在同样的理论水平上进行了IRC计算;CCSD(T)结合6-311G**基组对于驻点进行单点能及相对能量的计算;根据振动模式分析来阐明三线态势能面上各驻点之间的变化,并与单线态势能面进行比较.计算结果表明,三线态HFSiS分子存在6种异构体,3HFSiS结构在动力学和热力学上都是最稳定的,实验上应该可以观测到;在两组键旋转异构体当中,结构-2具有一定的动力学稳定性,而结构-1动力学稳定性较差;3SiSHF在动力学上和热力学上都是最不稳定的结构.

Theoretical Study on the Structures and Stability of HFSiS System

The structures and stability of triplet HFSiS system were investigated by density functional theory(DFT)in detail. The optimized geometrical parameters and vibrational frequencies of all species were obtained at the level of B3LYP/6-311G~(**) and the assignments of them were performed. At the same theoretical level, IRC calculations were carried. In addition, the singlet-point energies and relative energies were calculated by high level electron-correlation CCSD(T)/6-311G~(**). The isomerized and dissociated processes were explained by vibrational mode analysis method. The triplet PES is compared to the singlet one. The results are as the following: there are six isomers on the triplet PES. Moreover, ~3HFSiS is found to be the most thermodynamically and kinetically stable and is able to be observed in experiments. Structures-2 are the more stable ones between the two group bond cycled isomers and are predicted to be detected. ~3SiSHF is the most unstable isomer in thermodynamics and kinetics.