Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5417967 | Journal of Molecular Structure: THEOCHEM | 2008 | 5 Pages |
Abstract
The reactions of Pd+ and Pt+ with CS2 have been investigated at B3LYP, CCSD(T) and QCISD(T) levels of theory. Both Pd+ and Pt+ are found to be able to activate the C-S bond in CS2 and produce the products PdS+ and PtS+ through insertion-elimination mechanism. For both Pd+ and Pt+ the spin-forbidden reaction 2M+ + CS2 â 4MS+ + CS is found to be energetically more favorable than the spin-allowed reaction 2M+ + CS2 â 2MS+ + CS. According to the identified reaction mechanisms and PESs, the doublet-quartet surface-crossing is presumed to occur at the exit channel of the reaction. The reactions of Ni+, Pd+ and Pt+ with CS2 are systematically compared in reaction mechanism and potential energy surface. Although all these reactions exhibit obvious endothermic feature, comparisons of these reactions indicate that the reaction of Pt+ with CS2 is energetically much more favorable. The calculated results well rationalize the experimental observations.
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Tao Hong Li, Chuan Ming Wang, Shi Wen Yu, Xiang Yi Liu, Hui Fu, Xiao Guang Xie,