Table 4.
Correlation of the volume occupied in a 500 psec molecular dynamics computer simulation by the substrate parts to the sign of ΔR–SΔS‡
| 3-hexanol positive ΔR–SΔS‡ | 2-butanol negative ΔR–SΔS‡ | 3-methyl-2-butanol negative ΔR–SΔS‡ | 3,3-dimethyl-2-butanol negative ΔR–SΔS‡ | |||||||||
| al | ac | es | al | ac | es | al | ac | es | al | ac | es | |
| V10–500 psec | Y | N | N | Y | — | Y | N | Y | Y | — | N | N |
| V50–500 psec | Y | — | Y | Y | Y | Y | N | Y | Y | — | N | N |
| V50–500 psecTS | Y | N | Y | Y | N | N | N | Y | Y | N | N | N |
V10–500 psec, accumulated volume occupied by the substrate from time 10 ps in the MD simulation. V50–500 psec, accumulated volume occupied by the substrate from time 50 psec in the MD simulation. V50–500 psecTS, including only reactive TS sample structures from the MD-simulations. al, alcohol part of substrate. ac, acyl part of substrate. es, ester part of substrate. Y, yes. N, no. —, volume difference negligible (≤3 Å3).