Table 4.

Free energies of solvation and activation in water (in kcal/mol), and energies of activation in the gas phase, for the acetate + DCE reaction obtained from EVB and from M06-2X geometries. ‘RS’ and ‘TS’ stand for the reactant ion-molecule complex and the transition state, respectively. The experimental free energy of activation in water is 28.2 kcal/mol.²⁴,²⁷,²³⁰

Method	$\mathrm{\Delta }{X}_g^{\ne }$	$\mathrm{\Delta }{G}_S^{RS}$	$\mathrm{\Delta }{G}_S^{TS}$	$\mathrm{\Delta }{G}_w^{\ne }$
Optimized geometries at SM8	16.9a	−58.1	−53.4	21.6
Molecular dynamics on EVB PES21,28	2.0b	−77.8c	−54.9c	24.9d
SM8 on stationary point EVB geometries	2.3e	−58.0	−73.7	−13.4
SM8 on sampled EVB geometriesf	−6.2e	−64.8	−58.3	0.3

^a $\mathrm{\Delta }{V}_g^{\ne }$ calculated at the G3SX//M06-2X level.

^b $\mathrm{\Delta }{G}_g^{\ne }$ derived from columns 3, 4, and 5 and eq 11.

^cTaken from Ref. 28.

^dTaken from Ref. 21.

^e $\mathrm{\Delta }{V}_g^{\ne }$ calculated from the ground-state EVB PES.

^fRepresentative geometries of the molecular dynamics trajectory sampling presented in Figure 1(a) of Ref. 21.