Wang Xiaoli, Wang Yongcheng, Li Shuang, Zhang Yuwei, Ma Panpan
College of Chemistry and Chemical Engineering, Northwest Normal University Lanzhou, Gansu 730070, P.R. China.
J Phys Chem A. 2016 Jul 21;120(28):5457-63. doi: 10.1021/acs.jpca.6b04733. Epub 2016 Jul 12.
To gain a deeper understanding of the reaction mechanisms of Ti with acetonitrile molecules, the triplet and singlet spin-state potential energy surfaces (PESs) has been investigated at B3LYP level of density functional theory (DFT). Crossing points between the different PESs and possible spin inversion processes are discussed by spin-orbit coupling (SOC) calculation. In addition, the bonding properties of the species along the reaction were analyzed by electron localization function (ELF), atoms in molecules (AIM) and natural bond orbital (NBO). The results showed that acetonitrile activation by Ti is a typical spin-forbidden process; larger SOC (by 220.12 cm(-1)) and the possibility of crossing between triplet and singlet imply that intersystem crossing (ISC) would occur near the minimum energy crossing point (MECP) during the transfer of the hydrogen atom.
为了更深入地理解钛与乙腈分子的反应机理，在密度泛函理论（DFT）的B3LYP水平上研究了三重态和单重态自旋态势能面（PESs）。通过自旋轨道耦合（SOC）计算讨论了不同PESs之间的交叉点和可能的自旋反转过程。此外，通过电子定域函数（ELF）、分子中的原子（AIM）和自然键轨道（NBO）分析了反应过程中各物种的键合性质。结果表明，钛对乙腈的活化是一个典型的自旋禁阻过程；较大的SOC（220.12 cm(-1)）以及三重态和单重态之间交叉的可能性意味着在氢原子转移过程中，体系间交叉（ISC）将在最低能量交叉点（MECP）附近发生。
