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To elucidate the mechanisms of Zr + reacting with COS,both the quartet and doublet potential energy surfaces (PESs) for reactions of Zr + (4 F,2 D) with COS in the gas phase have been investigated in detail by means of density functional method (B3LYP).To obtain more accurate results,the coupled cluster single-point calculations (CCSD(T)) using B3LYP optimized geometries were performed.For the C-O bond activation,the calculated results indicate that both the quartet and doublet states proceed via an insertion-elimination mechanism.For the C-S bond activation,the quartet reaction has an insertion-elimination mechanism,but the doublet reaction is a direct abstraction of the sulfur atom by Zr +.The C-S bond activation is found to be energetically more favorable than the C-O bond activation.It is found that the reaction of the 4 F gound state of Zr + to yield ZrO + is spin-forbidden (Zr + (4 F) + COS (1 Σ) → ZrO + (2) + CS (1 Σ)) and the crossing points were approximately determined.All the results have been compared with the existing experimental and theoretical data.
To elucidate the mechanisms of Zr + reacting with COS, both the quartet and doublet potential energy surfaces (PESs) for reactions of Zr + (4 F, 2 D) with COS in the gas phase have been investigated in detail by means of density functional method (B3LYP). To obtain more accurate results, the coupled cluster single-point calculations (CCSD (T)) using B3LYP optimized geometries were performed. For the CO bond activation, the calculated results indicate that both both quartet and doublet states proceed through an insertion-elimination mechanism. For the CS bond activation, the quartet reaction has an insertion-elimination mechanism, but the doublet reaction is a direct abstraction of the sulfur atom by Zr +. The CS bond activation is found to be energetically more favorable than the CO bond activation. It is found that the reaction of the 4 F gound state of Zr + to yield ZrO + is spin-forbidden (Zr + (4 F) + COS (1 Σ) → ZrO + (2) + CS 1 Σ)) and the crossing points were to approximately determined. Al l the results have been compared with the existing experimental and theoretical data.