Gibbs free energy of activation (ΔG^≠, kcal mol⁻¹), diffusion rate constant (k_D, M⁻¹ s⁻¹), TST thermal rate constant (k_T, M⁻¹ s⁻¹), Eckart-tunneling-corrected rate constants (k_eck, M⁻¹ s⁻¹), diffusion-corrected apparent rate constants (k_app, M⁻¹ s⁻¹) and branching ratio Γ (%) at 298.15 K for the FHT, RAF and SET mechanism of the rosmarinate mono-anion (RA⁻) with CH₃OO˙ radicals in water calculated at the M05-2X/6-311++G(2df,2p) level of theory. The values in parentheses correspond to the results obtained in the PEA phase.

Position	ΔG≠	k D	k T	k eck	k app	Γ
FHT
O3H	19.1 (18.0)	2.41 × 109 (2.36 × 109)	3.52 × 102 (3.74 × 103)	8.10 × 104 (1.34 × 105)	3.52 × 102 (3.74 × 103)	7.84
O4H	18.6	2.40 × 109	8.61 × 102	2.07 × 105	8.61 × 102	19.17
O7H	18.3 (19.0)	2.39 × 109 (2.35 × 109)	3.22 × 103 (1.73 × 103)	1.72 × 106 (1.65 × 105)	3.22 × 103 (1.73 × 103)	71.60
O8H	21.1	2.40 × 109	6.20 × 101	7.07 × 104	6.20 × 101	1.38
RAF
C20	22.3 (25.9)	1.97 × 109 (1.94 × 109)	2.39 × 10−2 (2.70 × 10−4)	3.42 × 10−2 (4.24 × 10−4)	2.39 × 10−2 (2.7 × 10−4)	0.00
C21	24.4	1.92 × 109	8.79 × 10−4	1.65 × 10−3	8.79 × 10−4	0.00
SET
	40.4 (104.5)	7.88 × 109 (8.59 × 109)	3.41 × 10−16 (3.77 × 10−63)	—	3.41 × 10−16 (3.77 × 10−63)	0.00