A theoretical study on the gas phase reaction of La+ with CS2

A theoretical study on the gas phase reaction of Pd+ and Pt+ with CS2

“…The relative energies calculated at B3LYP, CCSD(T) and QCISD(T) levels are collected in Table 1. For most species, the relative energies at the three levels are close and the applications of these methods in many previous studies on metal and sulfur-containing systems show that they can provide reasonable accurate energetic results [14,16,[27][28][29][30][31][32][33]. Unless otherwise specified, the energies discussed below refer to the results obtained at CCSD (T) level and the potential energy diagrams for the reactions are shown in Figs.…”

“…The barriers of this step for them are 40.4 and 44.1 kJ/mol, respectively. Although 4 Pd-IM4 and 4 Pt-IM4 are strikingly similar to the species found in the reaction of La + with CS 2 [16], this mechanism is completely different from the abstraction-insertion mechanism in the case of La + . Such mechanism was also found in the reactions of Fe + [11] but not found for Ni + [14].…”

“…1, in the two complexes the metal atoms coordinate the carbon atom and they are stabilized by 188.8 and 143.2 kJ/mol, respectively, relative to the quartet reactants. Such complex was not found for the reaction of Ni + [14] but identified in the reaction of La + with CS 2 [16]. It should be noted that obvious electron transfer from La + to CS 2 was found so that the La + -CS 2 complex can be understood as a molecular dication like La 2+ -CS 2 À , whereas such behavior is not found in 4 Pd-IM3 and 4 Pt-IM3.…”

“…This obviously indicates that the early metal cations are more reactive than the late cations. The results of our recent study on the reaction of La + with CS 2 [16] has revealed that La + exhibits some similar behaviors to some 3d metals, such as V + [6] and Fe + [11], and also shows some differences from these metals. Moreover, the calculated potential energy surfaces suggest that the spin-allowed reaction is highly endothermic whereas the spin-forbidden reaction is notably exothermic.…”

二氯卡宾与甲醇及甲硫醇插入与氢抽提反应的量子化学计算

“…根据Bader等 [22,23] 提出的电子密度拓扑分析理论, 一个分子中电子密度分布的拓扑性质取决于电子密 度的梯度矢量场∇ρ(r)和Laplacian 量∇ 2 ρ(r). 一般来 说, 键鞍点处电子密度ρ(r c )的大小与化学键的强弱有 近年来, 反应体系势能面间 "系间串越"现象的 理论研究引起了人们的广泛关注 [24,25] . 从图…”