1

S1. Free energy of hydrogen atom, proton and electron

The free energies of particles like hydrogen atom, proton and electron in different medium, which are used

in this work, are given in the following Table 1.s. We have collected them from Jan Rimarck’s work done in

2010 [41].

Table 1.s. Solvation free energies ΔG°solv of hydrogen atom H●, proton H+ and electron e- in kJ/mol

Solvent ε ΔG°solv(H●) ΔG°solv(H+) ΔG°solv(e-)Cyclohexane 2.02 -20 -772.0 0.2Benzene 2.28 -20 -968.4 -13.0Dichloromethane 8.93 -20 -1423.5 -338.0Methanol 32.7 -20 -1012.1 -84.0Water 78.4 27.7 -995.9 -99.3

S2. Relaxed potential energy surface of vibrational well

The vibrational potential wells in Figure 1.s. are obtained by scanning O-H bond at B3LYP/6-31G level

of theory. In this we have calculated the potential energy of the O-H bond for 30 points with a step of

0.075Ǻ starting from 0.675 Ǻ for all the molecules studied. It has been done for either site (position 3 and

4). Then we have set the molecular geometry of the lowest point of the well and the highest point (30th

point) of all the potential wells to make optimization at B3LYP/6-31+G(d,p) level of theory. This has

allowed us to calculate the depth of each well which is the energy range of both geometries found. We have

done calculations only in benzene, methanol and water to find energy range which are collected in Table 1.s.

The data displayed in Table 2.s. show that the well in site 4 is deeper than the one in site 3 for all the

molecular trio (CAPE, MBC and BC). These results agree with the BDE parameter in our previous work [7]

which states that, it is easy to lift hydrogen atom from site 3 rather than the one in site 4 in vacuum as in

solvents. It is noticeable that, the higher the dielectric constant the lower the depth of vibrational potential

well. Therefore, solvents contribute to fill in well, in the other words; they contribute to diminish the depth

of vibrational potential well. The depths of vibrational potential of well of molecules are ordered as follow:

depth(CAPE3) ~ depth(MBC3) < depth(BC3) < depth(P4HC) < depth(P3HC). This order is in good

agreement with the one obtained by BDE3 [7]. In solvents, CAPE loses its AA power, because it digs

forward its well compared to BC and MBC molecules. Thus, the depth can be used to describe antioxidant

activity of phenolic compounds.

S3. O-H bond vibration

The frequency is defined as the speed of vibration. From our calculation, we have collected the

vibrational frequency data of O-H bond of all molecules studied in both position (3 and 4) displayed in our

previous work [7]. The value of the vibrational frequency O-H bond of CAPE is 3842.9cm-1 in site 3 and

3774.5cm-1 in site 4. However, the IR spectrum done by Son et al [5] showed a peak for phenolic -OH at

3490cm-1. This value is lower than that found by calculation; because Son has found it by X-ray diffraction

on a single crystal of CAPE. Since in that crystal, each CAPE sees the other ones, then it is normal that the

2

frequency value of O-H bond reduces; this is because all O-H bonds are choked by the surrounding

molecules.

Table 2.s. vibrational potential depth of O-H bond of CAPEn (n=3,4) and its derivative in conformer BSolvents Vacuum Benzene Methanol WaterCAPE3 0.1880 0.1880 0.1872 0.1870CAPE4 0.1988 0.1953 0.1910 0.1908MBC3 0.1880 0.1880 0.1866 0.1869MBC4 0.1984 0.1949 0.1908 0.1904BC3 0.1888 0.1887 0.1870 0.1868BC4 0.1988 0.1951 0.1905 0.1902P3HC 0.2027 0.2022 0.2008 0.2007P4HC 0.1953 0.1949 0.1932 0.1930

0,5 1,0 1,5 2,0 2,5 3,0

-958,10

-958,05

-958,00

-957,95

-957,90

-957,85

-957,80

-957,75

-957,70

0.18

80au

B-CAPE3

En

erg

y in

a.u

.

O3-H

3 bond distance

0,5 1,0 1,5 2,0 2,5 3,0

-958,10

-958,05

-958,00

-957,95

-957,90

-957,85

-957,80

-957,75

-957,70

0.19

88au

B-CAPE4

En

ergy

in a

.u.

O4-H

4 bond distance

0,5 1,0 1,5 2,0 2,5 3,0-843,80

-843,75

-843,70

-843,65

-843,60

-843,55

-843,50

-843,45

-843,40

0.18

78au

B-MBC3

En

erg

y in

a.u

.

O3-H

3 bond distance

0,5 1,0 1,5 2,0 2,5 3,0-843,80

-843,75

-843,70

-843,65

-843,60

-843,55

-843,50

-843,45

-843,40

0.19

85au

B-MBC4

Ene

rgy

in a

.u.

O4-H4 bond distance

0,5 1,0 1,5 2,0 2,5 3,0-918,80

-918,75

-918,70

-918,65

-918,60

-918,55

-918,50

-918,45

-918,40

0.18

88au

B-BC3

En

ergy

in a

.u.

O3-H

3 bond distance

0,5 1,0 1,5 2,0 2,5 3,0-918,80

-918,75

-918,70

-918,65

-918,60

-918,55

-918,50

-918,45

-918,40

0.19

88au

B-BC4

En

erg

y in

a.u

.

O4-H4 bond distance

3

0,5 1,0 1,5 2,0 2,5 3,0

-882,90

-882,85

-882,80

-882,75

-882,70

-882,65

-882,60

-882,55

-882,50

0.20

27au

B-P3HC

En

ergy

in a

.u.

O3-H

3 bond distance

0,5 1,0 1,5 2,0 2,5 3,0

-882,90

-882,85

-882,80

-882,75

-882,70

-882,65

-882,60

-882,55

-882,50

0.19

53au

B-P4HC

Ene

rgy

in a

.u.

O4-H

4 bond distance

Fig.1.s. RPES obtained from hydrogen displacement of O-H bonding

1,01,1

1,21,3

1,41,5

1,61,7

1,8

-994,630

-994,625

-994,620

-994,615

-994,610

-994,605

-994,600

-994,595

106108

110112

114116

118120

122

En

ergy

in a

.u.

C 3-O

3-H 3

(°)

R(O3 -H

3 ) in Angström

B-MBC + HO.2

1,01,1

1,21,3

1,41,5

1,61,7

1,8

-1069,635

-1069,630

-1069,625

-1069,620

-1069,615

-1069,610

-1069,605

-1069,600

106108

110112

114116

118120

122

En

ergy

in a

.u.

C 3-O 3

-H 3 (°

)R(O

3 -H3 ) in Angström

B-BC + HO.2

1,0 1,1 1,2 1,3 1,41,5

1,61,7

1,81,9

-1033,75

-1033,74

-1033,73

-1033,72

-1033,71

-1033,70

-1033,69

-1033,68

104106

108110

112114

116118

120

Ene

rgy

(au

)

C 3-O

3-H

3 (°

)

R(O3-H

3) in Angström

B-P3HC + HO.2

1,0 1,1 1,2 1,3 1,4 1,5 1,6 1,7 1,8 1,9 2,0

-1034,06

-1034,05

-1034,04

-1034,03

-1034,02

-1034,01

-1034,00

104106

108110

112114

116118

120

Ene

rgy

in a

.u.

C 4-O 4

-H 4 (°

)

R(O4-H

4) in Angström

B-P4HC + HO.2

Fig.2.s. 3D-RPES of the reaction of B-MBC with HO2●, B-BC with HO2

●, B-P3HC with HO2●

and B-P4HC with HO2●

4

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

200

300

400

500

600

700

800 B-CAPE B-MBC B-BC B-P3HC

Fre

e en

erg

y of

rea

ctio

n

1 3 in

kJ/

mo

l

solvents

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

100

200

300

400

500

600

700

800 B-CAPE B-MBC B-BC B-P4HC

Fre

e e

ner

gy o

f re

act

ion 1 4

in k

J/m

ol

solvents

Fig.6.s. Free energy of reaction Γ13 (right) and reaction Γ1

4 (left) of B-CAPE, B-P4HC, P3HC, B-MBC and B-BC each other in the presence of radical HO2

● in different media

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

0

100

200

300

400

500

600B-MBC reaction A

3 (CPCET)

reaction B1 (ET-PT)

reaction 2

3 (SPLET)

Fre

e en

ergy

in k

J/m

ol

solvents

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

-200

-150

-100

-50

0

50

B-MBC

reaction A3 (CPCET)

reaction 1

3 (PT-ET)F

ree

en

erg

y in

kJ/

mo

l

solvents

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

0

100

200

300

400

500

600B-BC reaction A

3 (CPCET)

reaction B1 (ET-PT)

reaction 2

3 (SPLET)

Fre

e e

ne

rgy

in k

J/m

ol

solvents

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

-200

-150

-100

-50

0

50

B-BC

reaction A3 (CPCET)

reaction 1

3 (PT-ET)

Fre

e e

ne

rgy

in k

J/m

ol

solvents

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

0

100

200

300

400

500

600 B-P3HC reaction A3 (CPCET)

reaction B1 (ET-PT)

reaction 2

3 (SPLET)

Fre

e en

erg

y in

kJ/

mol

solvents

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

-150

-100

-50

0

50

100

B-P3HC

reaction A3 (CPCET)

reaction 1

3 (PT-ET)

Fre

e e

nerg

y in

kJ/

mo

l

solvents

5

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

0

100

200

300

400

500

600B-P4HC reaction A

4 (CPCET)

reaction B1 (ET-PT)

reaction 2

4 (SPLET)

Fre

e en

erg

y in

kJ/

mol

solvents

Vacuum

CyclohexaneBenzene

DichloromethaneMethanol

Water

-200

-150

-100

-50

0

50

100

B-P4HC

reaction A3 (CPCET)

reaction 1

3 (PT-ET)

Fre

e e

nerg

y in

kJ/

mo

l

solvents

Fig.9.s. Free energy of reaction An, B1

n and Γ1 (n=3,4) of B-P4HC, P3HC, B-MBC and B-BC in the presence of radical HO2

● (right) and radical O2●- (left) in different media.

S4. The equilibrium geometry coordinates of transition state

i. The transition state coordinates of reaction involving BCAPE3 + HO2● in vacuum

C 5.01657200 -2.12048300 0.83866600C 3.63349900 -2.19959600 0.79510500C 2.81257600 -1.06921000 0.49173900C 3.42052400 0.15419800 0.21944500C 4.82705200 0.27600500 0.25916900C 5.62451900 -0.89267000 0.57967800H 2.84874900 1.04502400 -0.01684600O 5.50209000 1.36059100 0.02737900O 6.94915700 -0.73880500 0.61605800H 7.11178400 0.20458000 0.40665200H 5.63111100 -2.98226600 1.07328800H 3.14939500 -3.15116500 0.99312400C 1.36680100 -1.26749800 0.47629400H 1.01508000 -2.27686000 0.68246300C 0.41696500 -0.34254300 0.24087000H 0.63913200 0.69756800 0.02742400C -1.00976000 -0.73066600 0.27276700O -1.43668500 -1.84874100 0.49410100O -1.80105400 0.33831900 0.02049800C -3.22211100 0.08488500 0.02966300H -3.46005100 -0.66875900 -0.72772900H -3.50990400 -0.32548800 1.00264700C -3.92429300 1.41136400 -0.25359300H -3.57773000 1.79362100 -1.21988400H -3.61940600 2.13859700 0.50685400C -5.43025000 1.25199300 -0.25787300C -6.11506900 0.93807000 -1.43919400H -5.55933800 0.84217200 -2.36901400C -7.49825700 0.75550400 -1.43803600H -8.01191100 0.51701600 -2.36496700C -8.22020200 0.88401700 -0.25058700H -9.29732300 0.74531300 -0.24837300C -7.55032200 1.19756000 0.93304500H -8.10483700 1.30484200 1.86090800C -6.16717300 1.37924500 0.92708100H -5.65220000 1.62896800 1.85174800H 4.63667000 2.46083300 0.05002600O 3.70456300 3.46785500 0.07625700O 3.72304500 3.83626500 -1.30417000H 3.43065900 4.76023700 -1.24025600

ii. The transition state coordinates of reaction involving BCAPE3 + HO2● in benzene

C -5.36825600 -2.11534700 0.16162500C -3.99913300 -2.29954900 0.16285300C -3.06788400 -1.20942200 0.01802000C -3.55245700 0.07830800 -0.13229600C -4.95322100 0.31566900 -0.13626200C -5.86444500 -0.81720300 0.01205400H -2.91036000 0.94454000 -0.25728700

6

O -5.50794000 1.46680000 -0.26259000O -7.16550600 -0.56296300 0.00003300H -7.26350900 0.40577600 -0.11715300H -6.05681000 -2.94507800 0.27107800H -3.60000800 -3.30242700 0.27773400C -1.64406600 -1.53652400 0.03805600H -1.39256400 -2.59180700 0.11978500C -0.61641400 -0.66972600 -0.02802700H -0.74908800 0.40425600 -0.10212900C 0.77630400 -1.17156300 0.00705700O 1.10485800 -2.34298000 0.09020800O 1.65151500 -0.14898100 -0.06406300C 3.05502100 -0.50119500 -0.03078000H 3.26063700 -1.06372500 0.88477900H 3.28200100 -1.15022100 -0.88234100C 3.85114700 0.80024500 -0.08498100H 3.55211600 1.42975900 0.75983500H 3.58633900 1.33834600 -1.00133300C 5.34177900 0.53655100 -0.04148700C 6.01772300 0.45128500 1.18354100H 5.46794500 0.60622100 2.10867500C 7.38588100 0.17847400 1.22879200H 7.89325000 0.12126000 2.18749800C 8.10106400 -0.01516400 0.04510500H 9.16626600 -0.22392800 0.07831400C 7.43922000 0.06678300 -1.18177500H 7.98826000 -0.07763000 -2.10779200C 6.07084100 0.33980200 -1.22245500H 5.56291500 0.40777400 -2.18138800H -4.51615800 2.44013100 -0.43286600O -3.46942400 3.31345700 -0.59178200O -3.29204800 3.77550000 0.78722700H -3.68151100 4.66154400 0.72809000

iii. The transition state coordinates of reaction involving BCAPE3 + HO2● in water

C -3.10431800 -1.16893800 0.01035500C -3.57676100 0.13438900 -0.07862500C -4.96923000 0.38795100 -0.10657900C -5.88685200 -0.74068400 -0.05423200C -5.41552200 -2.05415200 0.03689000C -4.05245400 -2.26343300 0.06741200H -2.90181200 0.98894000 -0.11088200O -5.52657700 1.55010400 -0.18213800H -4.56089600 2.53456600 -0.35925200O -7.18741300 -0.49331100 -0.08092400H -7.32207300 0.47838200 -0.14663000H -6.10972500 -2.88569000 0.08128800H -3.66079800 -3.27621900 0.14197300C -1.68704400 -1.52380800 0.06607300H -1.47825200 -2.58553400 0.22785400C -0.63045600 -0.69508700 -0.07094700H -0.72790900 0.37956100 -0.24254000C 0.75782800 -1.21200100 0.06085500O 1.06498000 -2.38977700 0.24197700O 1.65109200 -0.22032800 -0.05409400C 3.06263800 -0.56448100 0.17662900H 3.18971600 -0.84677500 1.26985800H 3.37805400 -1.45082800 -0.46674300C 3.85223900 0.73161500 -0.20051300H 3.57847100 1.55951300 0.50857600H 3.56517600 1.04792500 -1.23832600C 5.34538800 0.47031500 -0.13421700C 5.98780100 0.37991500 1.11951300H 5.40075700 0.48241000 2.02923700C 7.37086100 0.15535700 1.19771800H 7.85200400 0.08334500 2.16522900C 8.12500100 0.02657200 0.02764300H 9.20260800 -0.13579900 0.08525800C 7.49618900 0.13475400 -1.21825700H 8.08262900 0.04202400 -2.13869400C 6.12281000 0.34942400 -1.30134700H 5.64127000 0.44157100 -2.26897700O -3.52017900 3.40859400 -0.55053400O -3.02507100 3.58005800 0.83329300H -3.51257600 4.38364000 1.11188600

iv. The transition state coordinates of reaction involving BCAPE4 + HO2● in vacuum

7

C 4.71937200 2.00610800 0.00368400C 3.35469900 2.19601700 0.00149700C 2.44877100 1.09937300 -0.00114400C 2.98298200 -0.20998200 -0.00243000C 4.34919200 -0.41822200 -0.00062400C 5.27264700 0.69411800 0.00384400H 2.31761500 -1.06943700 -0.00505300O 4.93946800 -1.64005100 -0.00272300H 4.27795700 -2.34528100 -0.00570600O 6.54990900 0.52326200 0.00829800H 5.41272800 2.84007100 0.00591000H 2.95190900 3.20471500 0.00184200C 1.02683600 1.37794000 -0.00258700H 0.74655900 2.43001800 -0.00217800C 0.00641700 0.48756700 -0.00425200H 0.15495200 -0.58709900 -0.00479300C -1.39142600 0.95865800 -0.00517300O -1.75257000 2.12358900 -0.00488800O -2.25359200 -0.08914500 -0.00650100C -3.66207100 0.24167500 -0.00672300H -3.88613500 0.84714900 0.87690300H -3.88598800 0.84568700 -0.89140400C -4.44117900 -1.07261400 -0.00575800H -4.14817100 -1.65614600 0.87424800H -4.15407800 -1.65429400 -0.88893200C -5.93724200 -0.83228900 -0.00060800C -6.63968600 -0.70378000 1.20669700H -6.10701100 -0.80727800 2.14929900C -8.01403000 -0.45237200 1.21421600H -8.54039800 -0.36001500 2.16002200C -8.71013200 -0.32545600 0.00912000H -9.77900200 -0.13284000 0.01287500C -8.02259600 -0.45280000 -1.20082700H -8.55564000 -0.36075400 -2.14291600C -6.64822300 -0.70425200 -1.20294700H -6.12222200 -0.80815000 -2.14924300H 7.18278200 -0.74774800 0.00342400O 7.98546400 -1.99554300 -0.00144400O 9.30017200 -1.50328100 0.00388800H 9.81735000 -2.32735600 -0.00324900

v. The transition state coordinates of reaction involving BMBC3 + HO2● in vacuum

C 4.41770000 -2.07062600 0.62013800C 3.06218300 -2.34795700 0.53182200C 2.08667300 -1.32597400 0.31949600C 2.51154300 -0.00456600 0.18961400C 3.88217800 0.31630400 0.27708400C 4.84025600 -0.74734100 0.50043600H 1.81710700 0.81231100 0.02488000O 4.38994000 1.50624500 0.17111300O 6.12786700 -0.40514000 0.58474200H 6.14925100 0.56795700 0.47166400H 5.15085800 -2.85231200 0.78416000H 2.72283200 -3.37549300 0.62142300C 0.68732700 -1.73174200 0.24225500H 0.48746200 -2.79690600 0.34471200C -0.38649500 -0.93944600 0.06173100H -0.31961200 0.13750000 -0.05026900C -1.74003100 -1.53435700 0.01263300O -1.99649000 -2.72069000 0.11644200O -2.67661600 -0.57568400 -0.16232400C -4.04877500 -1.05058500 -0.23500800H -4.10391500 -1.79013300 -1.04294000H -4.28902000 -1.57228600 0.69379200C -4.92224300 0.13054300 -0.50753900H -4.64829900 0.69214600 -1.39959200C -5.98672800 0.53950700 0.19923100C -6.50081100 -0.12107900 1.45410600H -5.87327000 -0.94158300 1.80512200H -7.51168000 -0.51773500 1.29416100H -6.58095700 0.61378500 2.26478600C -6.78506500 1.74079600 -0.24525600H -6.38108000 2.18787100 -1.15714200H -7.83225500 1.46972000 -0.43247400H -6.79879500 2.51062300 0.53702700H 3.44481100 2.53782000 0.22191000O 2.43671400 3.49114800 0.30186100O 2.52520300 4.04288000 -1.00707700H 2.08718500 4.89856800 -0.86605300

8

vi. The transition state coordinates of reaction involving BMBC3 + HO2● in benzene

C 4.38780700 -2.09521300 0.37363400C 3.02630500 -2.33018100 0.34858500C 2.05465700 -1.26977000 0.26389200C 2.49352900 0.04213500 0.20908300C 3.88423100 0.32954600 0.22736800C 4.83679600 -0.77307100 0.31720100H 1.82055200 0.89211400 0.16443700O 4.38994000 1.50624500 0.17111300O 6.12739700 -0.46910700 0.33945300H 6.18823500 0.50855000 0.29220900H 5.10574600 -2.90449000 0.43890900H 2.66519200 -3.35283900 0.39360700C 0.64469400 -1.65241100 0.24194500H 0.43117500 -2.71268900 0.35926200C -0.41137200 -0.83347400 0.08250400H -0.31604600 0.23829800 -0.05560200C -1.78466000 -1.38970400 0.08090800O -2.06770200 -2.56825700 0.22246800O -2.69295300 -0.41337800 -0.09956500C -4.08891200 -0.83897600 -0.13795400H -4.17061500 -1.63538900 -0.88576700H -4.34565700 -1.26958600 0.83153300C -4.91327400 0.35073400 -0.50616700H -4.66045000 0.79115200 -1.46965400C -5.91538800 0.89816000 0.20009900C -6.39467400 0.41658800 1.54656800H -5.80251800 -0.40319500 1.95583900H -7.43736800 0.08036300 1.48346200H -6.37837700 1.24105300 2.26994100C -6.67178400 2.08550900 -0.34412100H -6.29250500 2.40148900 -1.31917300H -7.73963800 1.85425000 -0.44876900H -6.60461000 2.93713500 0.34476900H 3.44481100 2.53782000 0.22191000O 2.43671400 3.49114800 0.30186100O 2.29872600 3.85501300 -1.10837700H 2.70679300 4.73469500 -1.10457500

vii. The transition state coordinates of reaction involving BMBC3 + HO2● in water

C 4.39179800 -2.07458800 0.17932300C 3.04314400 -2.32473800 0.04227900C 2.05702100 -1.27219200 -0.03382500C 2.46901300 0.04452500 0.04493500C 3.84595100 0.34938600 0.19597500C 4.81491600 -0.74620000 0.25786300H 1.78019100 0.88319800 -0.01203200O 4.33460100 1.54370400 0.28117200O 6.09372400 -0.42909300 0.39423500H 6.15869000 0.54526300 0.43488600H 5.11916200 -2.87843500 0.22677500H 2.70055700 -3.36080500 -0.02435000C 0.66274200 -1.68068700 -0.18197800H 0.48535600 -2.75047100 -0.25330400C -0.42459700 -0.87405000 -0.22901400H -0.35914200 0.20582900 -0.15418300C -1.76909900 -1.45999500 -0.37432800O -2.02226900 -2.65407300 -0.50503500O -2.71542300 -0.50408900 -0.34582900C -4.10185400 -0.94400700 -0.49659700H -4.15499400 -1.53509100 -1.41678700H -4.34173900 -1.61005300 0.33774900C -4.96774700 0.26798100 -0.57535800H -4.75217600 0.91559300 -1.42426900C -5.96517500 0.61434900 0.27155700C -6.39820600 -0.17502900 1.47535900H -5.77694200 -1.04418800 1.68146900H -7.43682700 -0.51747800 1.35362700H -6.39164900 0.46859400 2.37337000C -6.76405800 1.86615000 0.02011600H -6.42577400 2.40720600 -0.86939000H -7.83053900 1.63012000 -0.10542000H -6.70233700 2.54429100 0.87993000H 3.37704200 2.54553200 0.28579700O 2.33645300 3.49772800 0.30539100

9

O 2.71922000 4.40012400 -0.92837600H 3.21759200 5.18106100 -0.43417600

viii. The transition state coordinates of reaction involving BMBC4 + HO2● in vacuum

C -3.66132300 -2.00234200 0.19991600C -2.30524700 -2.23901500 0.13824200C -1.36833600 -1.17834000 -0.00513200C -1.86214100 0.14429400 -0.08444900C -3.21911700 0.39911600 -0.02484800C -4.17405000 -0.67639000 0.12117000H -1.17266500 0.97730400 -0.19452600O -3.77148400 1.63652300 -0.09539100H -3.09058400 2.31576700 -0.19523800O -5.44355900 -0.46113300 0.17827100H -4.37807800 -2.80900500 0.30870100H -1.93335600 -3.25770100 0.19950900C 0.04239100 -1.50474600 -0.06448500H 0.29137100 -2.56248600 0.00299000C 1.08562400 -0.65138600 -0.19407500H 0.96805600 0.42448000 -0.26899900C 2.46862300 -1.16523000 -0.23896500O 2.79478900 -2.33956600 -0.17157400O 3.35495900 -0.14895800 -0.36489300C 4.76018100 -0.53274900 -0.43122200H 5.01577800 -1.06931500 0.48410800H 4.87154000 -1.23351400 -1.26634000C 5.56256000 0.70954700 -0.64582300H 5.32564200 1.24682600 -1.56355800C 6.53197600 1.20130500 0.14546000C 6.98498400 0.58945300 1.44895500H 6.39631800 -0.27676900 1.75536000H 6.93395500 1.33418100 2.25333100H 8.03477000 0.27546200 1.38076300C 7.27643200 2.45620500 -0.24471300H 6.91813600 2.86786200 -1.19225100H 7.16890900 3.22822900 0.52842500H 8.35208200 2.25846600 -0.34197700H -6.03064800 0.82930000 0.08538600O -6.78964000 2.10365500 0.00438300O -8.11990400 1.66551600 0.10748400H -8.60784700 2.50428000 0.03788500

ix. The transition state coordinates of reaction involving BBC3 + HO2● in vacuum

C 4.99429300 -1.72519000 0.91808100C 3.67678100 -2.15716500 0.93149800C 2.58463300 -1.27707700 0.66501900C 2.85080900 0.06262600 0.38186200C 4.17729700 0.53838500 0.36445800C 5.25806100 -0.38437500 0.64145700H 2.05999400 0.77623300 0.17693300O 4.54286300 1.76123400 0.11485700O 6.50166100 0.10236000 0.62323700H 6.40872000 1.05478500 0.41387600H 5.81824700 -2.39948300 1.12283800H 3.46122200 -3.19992500 1.14404800C 1.23868900 -1.83881300 0.69441500H 1.16188600 -2.89424100 0.94983300C 0.07953700 -1.20239400 0.43838500H 0.02306400 -0.15333000 0.16847500C -1.19796500 -1.94223300 0.51671600O -1.32154900 -3.11928300 0.80392000O -2.23911900 -1.12879100 0.22106500C -3.54758400 -1.75660600 0.26269300H -3.53731100 -2.62008500 -0.40917100H -3.72568400 -2.12857000 1.27580700C -4.57221700 -0.73493200 -0.14725300C -4.78918300 -0.45349400 -1.50216600H -4.21734600 -0.98710500 -2.25692300C -5.72830200 0.50206100 -1.88664800H -5.88873300 0.71005200 -2.94048000C -6.46554500 1.18642400 -0.91761900H -7.20088600 1.92786200 -1.21624200C -6.25791100 0.91216500 0.43461900H -6.83008300 1.43985800 1.19202100C -5.31456200 -0.04284700 0.81577900H -5.15327100 -0.25501000 1.86955200

10

H 3.48071100 2.67260000 0.15008500O 2.35983800 3.51564900 0.22439600O 2.29567600 3.95118100 -1.12482500H 1.75657000 4.75384600 -1.02658200

x. The transition state coordinates of reaction involving BBC3 + HO2● in benzene

C -4.95341400 -1.77752200 0.12853600C -3.62942400 -2.17469700 0.11742500C -2.54212100 -1.23948900 0.01786600C -2.82102500 0.11311100 -0.07102100C -4.16466400 0.56656400 -0.06733000C -5.24211900 -0.41175700 0.02674500H -2.05157500 0.87026600 -0.16950900O -4.51745600 1.79943500 -0.13415900O -6.48818300 0.04342600 0.02520500H -6.43368800 1.01895900 -0.05486600H -5.76330700 -2.49328100 0.19732100H -3.38821200 -3.23244100 0.18251500C -1.19125400 -1.78949900 0.01345700H -1.11782400 -2.87344100 0.03308600C -0.03646200 -1.09893700 0.00470900H 0.00725600 -0.01529000 0.01182100C 1.25667300 -1.82026300 0.00278500O 1.39067800 -3.03278500 -0.00419000O 2.28458900 -0.94952300 -0.00374700C 3.61749200 -1.53847100 -0.02331800H 3.70915400 -2.20076400 0.84482000H 3.71809300 -2.15321800 -0.92375900C 4.61666900 -0.42690700 0.00900600C 5.13514400 0.04057400 1.25572400H 4.81669900 -0.43358100 2.19617800C 6.04719500 1.09376100 1.28471300H 6.43807000 1.43803200 2.25107800C 6.45315300 1.69994200 0.07516800H 7.16618000 2.51767500 0.09080300C 5.95258600 1.25015900 -1.17130800H 6.27218600 1.70770000 -2.12272800C 5.03692200 0.18819400 -1.19759900H 4.64510200 -0.15958600 -2.16306900H -3.45764500 2.65864100 -0.43680900O -2.34161600 3.43951600 -0.77108800O -2.01498700 4.01169500 0.52950400H -2.31678800 4.92763300 0.39757100

xi. The transition state coordinates of reaction involving BBC3 + HO2● in water

C 2.55813200 -1.29423400 0.08702900C 2.79012500 0.05331900 0.34230900C 4.11236600 0.58058300 0.20924300C 5.21706600 -0.35030000 -0.04188000C 4.98805000 -1.72030500 -0.21513700C 3.68612600 -2.18318500 -0.17233600H 1.97316300 0.72124700 0.65476800O 4.44643600 1.82613900 0.30431900H 3.35886200 2.60176900 0.40728400O 6.45076400 0.13730500 -0.09435300H 6.41710100 1.11421300 0.04232700H 5.82342900 -2.38785100 -0.39683600H 3.48974700 -3.23214200 -0.32247700C 1.21485900 -1.86699300 0.06920000H 1.15403700 -2.95258000 0.05978000C 0.05884600 -1.16725800 0.02125600H 0.02764900 -0.07417700 -0.01109400C -1.24371500 -1.86579000 -0.02254500O -1.40175700 -3.07264400 -0.04595700O -2.26392300 -0.98050100 -0.01617700C -3.62004200 -1.54602000 -0.04312400H -3.71398400 -2.13675200 -0.95759700H -3.71918900 -2.19788800 0.82059900O 2.12725000 3.32960000 0.48951600O 2.18488900 4.14779500 -0.86017000

11

H 2.57256200 5.05766000 -0.52089800C -4.59816200 -0.41287200 -0.01076400C -5.07587500 0.08696900 1.20778000C -5.07034100 0.16242900 -1.20893700C -5.98630600 1.14730500 1.24923000H -4.71936400 -0.35628500 2.14371600C -5.99052100 1.21313500 -1.17063400H -4.71949100 -0.22629000 -2.15626100C -6.44978100 1.70748400 0.04930600H -6.34429400 1.51608100 2.19678600H -6.34401600 1.64656200 -2.10768000H -7.16046500 2.52928300 0.08020000

xii. The transition state coordinates of reaction involving BBC4 + HO2● in vacuum

C -4.17190700 1.96571800 0.00429500C -2.83479100 2.29886600 0.00194000C -1.81758400 1.30449300 -0.00043600C -2.20968600 -0.05421800 -0.00050300C -3.54618300 -0.40550200 0.00167600C -4.58263400 0.60248500 0.00419900H -1.45762200 -0.83892200 -0.00260000O -4.00405000 -1.68289300 0.00139200H -3.27210200 -2.31475700 -0.00010700O -5.83423200 0.29513900 0.00623100H -4.94955000 2.72168200 0.00611900H -2.54091600 3.34452100 0.00189800C -0.43293500 1.73154500 -0.00310000H -0.26462400 2.80717400 -0.00506900C 0.67435000 0.95201000 -0.00347300H 0.63855100 -0.13219000 -0.00114700C 2.01629500 1.56440800 -0.00716200O 2.25694700 2.76070900 -0.01094300O 2.97951500 0.60928700 -0.00593400C 4.35220500 1.09296800 -0.01060200H 4.49448100 1.71319200 -0.90006000H 4.49700600 1.72533500 0.86973100C 5.26969900 -0.09904100 -0.00346000C 5.68628000 -0.68406000 -1.20704200H 5.34877700 -0.26409100 -2.15127900C 6.52979600 -1.79702300 -1.20235700H 6.84756800 -2.23922000 -2.14219000C 6.96891800 -2.33634000 0.01027900H 7.62882700 -3.19907700 0.01548900C 6.56125700 -1.75841200 1.21592100H 6.90346800 -2.17041000 2.16088300C 5.71726200 -0.64565700 1.20686700H 5.40392600 -0.19586100 2.14567400H -6.31852900 -1.04084700 0.00364400O -6.97319200 -2.37191000 0.00119100O -8.33586400 -2.03492100 0.00273400H -8.75430900 -2.91324900 -0.00061200

xiii. The transition state coordinates of reaction involving BP3HC + HO2● in vacuum

C 5.68834000 -2.21519600 0.65230800C 4.29868700 -2.41439800 0.59094000C 3.40440500 -1.33528700 0.38112200C 3.93357200 -0.05833100 0.21678200C 5.34687200 0.16826600 0.28024300C 6.21971100 -0.95047900 0.51222800H 3.30295300 0.80806700 0.04475400O 5.85355300 1.34025800 0.12439300H 7.28592200 -0.75910900 0.56287000H 6.34222500 -3.06580600 0.81787400H 3.89504600 -3.41607700 0.70549400C 1.96752600 -1.62378700 0.33674600H 1.68326700 -2.67036900 0.43091700C 0.96404300 -0.74142500 0.19884600H 1.11854600 0.32819500 0.10335400C -0.43703800 -1.22026800 0.17737800O -0.79135000 -2.38070300 0.26741800O -1.29361000 -0.18162300 0.04339700C -2.69623000 -0.52287300 0.01074600H -2.89119700 -1.16415100 -0.85483100H -2.94955800 -1.09622200 0.90779300C -3.48288400 0.78387800 -0.06744400H -3.16215000 1.33520700 -0.95793400

12

H -3.22581500 1.40018000 0.80103000C -4.97530000 0.53121600 -0.11279100C -5.64167900 0.38805000 -1.33682300H -5.08335400 0.49208600 -2.26416900C -7.01075000 0.12262300 -1.38004700H -7.51053300 0.01994100 -2.33901000C -7.73662000 -0.00561400 -0.19501100H -8.80292800 -0.20910000 -0.22675600C -7.08479300 0.13434800 1.03123200H -7.64259300 0.04088500 1.95861500C -5.71580500 0.39999600 1.06957700H -5.21548800 0.51378500 2.02839700H 4.82854200 2.44162300 0.17801500O 3.81074200 3.41926200 0.24761600O 3.76262300 3.81460000 -1.12402600H 3.53265700 4.75333700 -1.02562600

xiv. The transition state coordinates of reaction involving BP4HC + HO2● in vacuum

C 5.23398900 -0.52912700 -0.02285700C 3.93184100 -0.96333700 -0.04975500C 2.83885100 -0.05279000 -0.04223100C 3.12960200 1.34444200 -0.02193900C 4.41978400 1.80279700 -0.00984900C 5.52743200 0.88032200 -0.00446200H 2.31224200 2.05818900 -0.02182500H 4.65122200 2.86243900 -0.00161800O 6.72441100 1.33345300 0.02241300H 6.07059000 -1.22114900 -0.02037200H 3.71904400 -2.02868400 -0.06598600C 1.49786300 -0.58147200 -0.04929000H 1.40325500 -1.66555800 -0.08050200C 0.33441600 0.11392000 -0.01756000H 0.28852500 1.19677500 0.02049500C -0.95369300 -0.60891900 -0.02767500O -1.08457000 -1.81827600 -0.07508000O -1.99089700 0.25897800 0.02634900C -3.30703100 -0.33704200 0.03094300H -3.45094500 -0.89871600 -0.89757800H -3.37701900 -1.04875200 0.85924100C -4.32376000 0.79398700 0.16898400H -4.18875000 1.49367900 -0.66304000H -4.11130800 1.34646400 1.09085500C -5.74169700 0.26181300 0.18737300C -6.46614600 0.10932200 -1.00206000H -6.01535400 0.41114400 -1.94452700C -7.75812800 -0.41710200 -0.99043300H -8.30592200 -0.52372100 -1.92230600C -8.34661100 -0.80083900 0.21545000H -9.35335000 -1.20792000 0.22666000C -7.63590900 -0.65327600 1.40760000H -8.08813100 -0.94477100 2.35118400C -6.34433100 -0.12647800 1.39123000H -5.79779300 -0.00961100 2.32408200H 7.74637600 0.25438700 -0.18057500O 8.70861200 -0.76490400 -0.42603600O 9.21853500 -0.92990900 0.89671900H 10.08003900 -1.33302200 0.69878300