Theoretical study of the reaction of Ni+ with OCS

Spin‐inversion mechanisms in the reactions of transition metal cations (Sc+, Ti+, V+, Cr+, Mn+, Fe+, Co+, Ni+, and Cu+) with OCS in the gas phase: A perspective from automated reaction path search calculations

“…The crossing points between the two potential energy surfaces with different spin multiplicities were also analyzed for the reactions of Sc + , Ti + , V + , Cr + , and Ni + using the approximation method proposed by Yoshizawa et al, where two potential energy profiles with different spin multiplicities are calculated along the IRC paths on the two spin states. Although the minimum crossing points for the reactions of Fe + , Co + , and Cu + have not been previously addressed, the overall reaction mechanisms obtained in the present automated reaction path search calculations are found to be generally similar to the results of the previous studies . Here, it may be important to provide a brief comment on the results for 6,4 Fe + + OCS reaction presented in Figure .…”

“…All the reaction path search calculations using the GRRM code were performed by interfacing with Gaussian 09 program package. [50] As most of previous theoretical calculations were done at the B3LYP level of theory with the standard 6-311 + G(d) basis sets, [37][38][39][40][41][42][43][44][45][46][47][48] we here employ the same level of theory, which enables quantitative comparisons to the previous calculations.…”

“…It should be emphasized that the previous experimental studies for these reactions were highly motivated by the biological importance of understanding of the production mechanisms of MS bond through the CS activation by transition metal atoms. In addition to these experimental studies, theoretical studies have also been performed in the past . However, the minimum crossing points between the potential energy surfaces with different spin multiplicities have not been fully characterized.…”

“…In addition to these experimental studies, theoretical studies have also been performed in the past. [37][38][39][40][41][42][43][44][45][46][47][48] However, the minimum crossing points between the potential energy surfaces with different spin multiplicities have not been fully characterized. Here we report the results of systematic reaction path search calculations and discuss the similarities and differences in spin-inversion mechanisms among the first-row 3d transition metal atom series.…”

Density functional theory analysis of carbonyl sulfide hydrolysis: effect of solvation and nucleophile variation

“…It is clear that the GGA-BLYP functional can provide satisfactory results, considering that our main goals in the present work are to examine the detailed hydrolysis mechanism and to calculate the relative energies of the species involved, not to calculate accurate bond energies. [28] b From [29] c From [30] d From [31] e From [32] Reaction mechanism…”