Table 1.
Rate constantsa | Experimentalb | kTSTc | kTST with QCPd | ktote |
---|---|---|---|---|
k1 | 1.7 × 105 | 1.7 × 105 | 1.3 × 106 | 3.6 × 105 |
k−1 | 5.6 × 105 | 5.6 × 105 | 4.3 × 106 | 1.2 × 106 |
k2 | 2.1 × 105 | 2.1 × 105 | 1.8 × 106 | 4.6 × 105 |
k−2 | 40 | 40 | 343.2 | 89.2 |
The EVB parameters used in all calculations for this table were V12 = 102.6 kcal/mol and Δ = 3.8 kcal/mol for the first step and V12 = 98.2 kcal/mol and Δ = −14.45 kcal/mol for the second step.
kTST was calculated with Eq. (4).
The QCP method includes the nuclear quantum effects of the transferring H.
ktot was calculated with Eq. (3) and includes nuclear quantum effects and barrier recrossings.
Rate constants given in s−1.