Theoretical investigation on reactivity of Ag and Au atoms toward CS2 in gas phase

The reaction mechanisms of Ag and Au atoms with CS2 on both doublet and quartet potential energy surfaces (PESs) have been investigated using UBPW91 and UCCSD(T) methods. The two studied reactions proceed via a similar insertion-elimination mechanism instead of a direct abstract mechanism. The reaction Ag + CS2 → SAgCS is endothermic by about 21.0 kcal/mol. But another reaction Au + CS2 → SAuCS is slightly exothermic by about 8.8 kcal/mol, which is different from the previous theoretical prediction. In the overall reactions, the rate-determining step is found to be the C-S bond cleavage step with a high-activation barrier of about 40 kcal/mol. The calculated vibration frequencies are in good agreement with the experiment values and show that the BPW91 method is very good for the calculation of small molecules containing Ag and Au. The reactivity of the two atoms toward CS2 is compared with those of the first-row transition-metal atoms. The present study provides a detailed picture of the C-S bond activation and cleavage in carbon disulfide mediated by second and the third row transition-metal atoms Ag and Au.