Erratum to “Thermochemistry and kinetics of the trans-N2H2+N reaction” [Chem. Phys. Lett. 557 (2013) 37–42]

Thermochemical and Kinetics of CH3SH + H Reactions: The Sensitivity of Coupling the Low and High-Level Methodologies

“…For the adiabatic barrier ( ΔV a G ,‡ ), the MP2 method, as expected, overestimates the barrier height (as pointed above), and the BB1K method differ from the highly correlated results by less than 1 kcal mol –1 . As discussed above, we have also shown previously that BB1K usually provides accurate thermochemical results for hydrogen abstraction reactions. ,, Also, in a recent review, Peverati and Truhlar have shown the excellent performance of BB1K for 76 barrier heights with comparable results to more recent functionals, such as M06-2X, M08-SO, M08-HX, and MN12-SX …”

“…When the value for the imaginary mode is too high, the barrier becomes narrower, which may lead to artificially enhanced tunneling effects, as will be explained in the following discussion. We have shown previously that the BB1K method produces imaginary frequencies for the transition states that are sufficiently close to the CCSD­(T) calculations. ,, …”

“…As discussed above, we have also shown previously that BB1K usually provides accurate thermochemical results for hydrogen abstraction reactions. 16,17,50 Also, in a recent review, Peverati and Truhlar 58 have shown the excellent performance of BB1K for 76 barrier heights with comparable results to more recent functionals, such as M06-2X, 20 M08-SO, 59 M08-HX, 59 and MN12-SX. 60 Both the aTdZ and aDdZ basis sets are suitable to perform the V mep and V a G calculations, since the difference between the calculated barriers is only 0.33 kcal mol −1 .…”

“…We have shown previously that the BB1K method produces imaginary frequencies for the transition states that are sufficiently close to the CCSD(T) calculations. 16,17,50 To verify if a multireference method is required for a reliable characterization of these structures, the T 1 diagnostic was calculated with the CCSD/aQdZ methodology at the optimized geometries obtained with the BB1K/aTdZ and MP2/6-311+G(d,p) approaches (Table 2). The highest T 1 diagnostic value is for the CH 2 SH molecule (0.019), and it is still below the limits proposed by Lee and Taylor 37 (0.02) and Rienstra-Kiracofe et al 38 (0.044).…”

“…In previous works, we have employed the dual-level methodology to calculate accurately the properties of several chemical reactions. ,,− In this work, with the experience gained from previous research, a rigorous analysis was carried out regarding the coupling of the low and high-level methods, in particular when calculating the thermochemical properties, and subsequent rate constant calculations. We have analyzed in which conditions this coupling can generate artificial tunneling and variational effects in the calculated rate constants.…”