Electronic supplementary information

for

Hydrogen atom transfer versus proton coupled electron transfer

mechanism of gallic acid with different peroxy radicals

Dejan Milenković1 · Jelena Đorović1 · Vladimir Petrović2 · Edina Avdović2 · Zoran

Marković1,3*

Fig. S1 SOMOs of the most stable radicals formed from the investigated GA in water

Fig. S2 Optimized structures of transition states for HAT mechanism. The distances between

C=O, O−H and H−O9 bonds are given in pm

Fig. S3 Optimized structures of transition states for PCET mechanism. The distances between

C=O, O−H and H−O9 bonds are given in pm

Fig. S4. Dependence of lnkTST and lnkZCT (M-1 s-1) on reciprocal temperature 1/T (K) in the HAT pathways of GA with peroxy radicals.

Fig. S5. Dependence of lnkTST and lnkZCT (M-1 s-1) on reciprocal temperature 1/T (K) in the PCET pathways of GA with peroxy radicals

Table S1. The imaginary frequencies for the all TSs HAT PCETWater

GA−3O· υi(cm-1)

υi(cm-1)

MP -2597.31 /EP -2603.88 /iPP -3108.10 /tBP -3214.80 /

GA−4O·

MP -2337.03 /EP -2318.43 /iPP -2713.52 /tBP -3256.56 /

GA−3O· Benzene

MP -2215.50 -3052.75EP -2247.66 -3108.38iPP -2483.25 -3166.58tBP -2484.36 -3305.57

GA−4O·

MP -2033.83 -3200.97EP -2111.28 -3216.50iPP -2246.58 -3282.17tBP -2502.26 -3406.97

Table S2. The calculated values of kinetic parameters for the reaction of monoanion of GA (GA−(OO-)−4O·) and free peroxy radicals.

ΔG≠

(kJ/mol)kTST

(M-1 s-1)kZCT

(M-1 s-1) γ

MP 27.9 8.04x107 1.64x109 2.04x101

EP 29.9 3.56x107 1.08x108 1.20x102

iPP 30.3 2.16x106 6.49x108 3.00x102

tBP 39.0 9.00x105 3.67x108 4.02x102