Appendix A

STRUCTURES
Fig.1. Structure and atom numbering scheme of 1, 2 – benzosemiquinone radical

Fig.2. Structure and atom numbering scheme of 1, 3 – benzosemiquinone radical

Fig.3. Structure and atom numbering scheme of 1, 4 – benzosemiquinone radical

Table 1. Calculated bond lengths and angles of 1, 2 -BSQ radical in its free form, on C 2V
symmetry (bond lengths in Å and angles in degrees)

Geometrical UB3LYP/ UB3LYP/ UB3LYP/

parameter 6-31+G 6-31++G EPR-II
C1-C2 1.4456 1.4456 1.4557
C1-C6 1.3843 1.3843 1.3880
C1-H7 1.0881 1.0881 1.0898
C2-C3 1.4965 1.4965 1.5219
C2-O12 1.2914 1.2915 1.2595
C3-C4 1.4456 1.4456 1.4557
C3-O11 1.2914 1.2915 1.2595
C4-C5 1.3843 1.3843 1.3880
C4-H8 1.0881 1.0881 1.0898
C5-C6 1.4269 1.4268 1.4294
C5-H9 1.0892 1.0892 1.0904
C6-H10 1.0892 1.0892 1.0904
C2-C1-C6 122.7086 122.7089 122.8812
C2-C1-H7 116.1032 116.1068 116.0204
C6-C1-H7 121.1882 121.1843 121.0985
C1-C2-C3 117.1636 117.1635 116.7567
C1-C2-O12 120.8059 120.8037 121.6931
C3-C2-O12 122.0305 122.0328 121.5502
C2-C3-C4 117.1636 117.1635 116.7567
C2-C3-O11 122.0305 122.0328 121.5502
C4-C3-O11 120.8059 120.8037 121.6931
C3-C4-C5 122.7086 122.7089 122.8812
C3-C4-H8 116.1032 116.1068 116.0204
C5-C4-H8 121.1882 121.1843 121.0985
C4-C5-C6 120.1278 120.1276 120.3622
C4-C5-H9 120.2741 120.2766 120.1654
C6-C5-H8 119.5981 119.5958 119.4724
C1-C6-C5 120.1278 120.1276 120.3622
C1-C6-H10 120.2741 120.2766 120.1654
C5-C6-H10 119.5981 119.5958 119.4724
Table 2. Calculated Atomic Charges and spin densities of 1, 2-BSQ

Atomic Charge Atomic Spin Densities

Atom UB3LYP/ UB3LYP/ UB3LYP/ UB3LYP/ UB3LYP/ UB3LYP/
6-31+G 6-31++G EPR-II 6-31+G 6-31++G EPR-II
C1 -0.003491 0.172215 -0.227618 0.095783 0.091924 0.111221
C2 -0.013526 -0.197087 0.145705 0.040164 0.043648 0.055674
C3 -0.013526 -0.197087 0.145705 0.040164 0.043648 0.055674
C4 -0.003491 0.172215 -0.227618 0.095783 0.091924 0.111221
C5 -0.186879 -0.262708 -0.138787 0.074623 0.078315 0.093045
C6 -0.186879 -0.262708 -0.138787 0.074623 0.078315 0.093045
H7 0.148574 0.191504 0.084945 -0.005553 -0.007650 -0.006634
H8 0.148574 0.191504 0.084945 -0.005553 -0.007650 -0.006634
H9 0.132860 0.158655 0.059666 -0.005146 -0.006259 -0.006207
H10 0.132860 0.158655 0.059666 -0.005146 -0.006259 -0.006207
O11 -0.577537 -0.562580 -0.423912 0.300128 0.300022 0.252900
O12 -0.577537 -0.562580 -0.423912 0.300128 0.300022 0.252900

Table 3. Calculated hyperfine coupling constants of 1, 2-BSQ radical in gas-phase with C 2V

symmetry using different basis sets in Gauss.

UB3LYP/ UB3LYP/ UB3LYP/

6-31+g 6-31++g EPR-II
Energy
-381.435 -381.436 -381.583
(Hartree)
<S2> 0.7745/ 0.7501 0.7745/0.7501 0.7758/0.7501
Dipole moment
6.6002 6.6021 5.4159
(debey)
C1 3.20766 3.21943 0.50399
C2 -1.76961 -1.77553 -4.60265
C3 -1.76961 -1.77553 -4.60265
C4 3.20766 3.21943 0.50399
C5 3.12442 3.13179 0.53501
C6 3.12442 3.13179 0.53501
H7 -2.67353 -2.66022 -2.76661
H8 -2.67353 -2.66022 -2.76661
H9 -2.41196 -2.40220 -2.66040
H10 -2.41196 -2.40220 -2.66040
O11 -13.90074 -13.89989 -6.69406
O12 -13.90074 -13.89989 -6.69406
Table 4. Calculated bond lengths and angles of 1, 3 -BSQ radical in its free form, on C s symmetry
(bond lengths in Å and angles in degrees)

Geometrical UB3LYP/ UB3LYP/ UB3LYP/

parameter 6-31+G 6-31++G EPR-II
C1-C2 1.4698 1.4698 1.4872
C1-C6 1.3970 1.3970 1.3987
C1-H12 1.0871 1.0871 1.0886
C2-C3 1.4191 1.4191 1.4281
C2-O11 1.3063 1.3064 1.2714
C3-C4 1.4191 1.4191 1.4281
C3-H7 1.0852 1.0852 1.0877
C4-C5 1.4699 1.4698 1.4872
C4-O10 1.3062 1.3064 1.2715
C5-C6 1.3970 1.3970 1.3987
C5-H8 1.0870 1.0870 1.0886
C6-H9 1.0892 1.0892 1.0911
C2-C1-C6 121.5694 121.5637 122.0522
C2-C1-H12 116.6520 116.6571 116.2972
C6-C1-H12 121.7786 121.7793 121.6506
C1-C2-C3 117.2108 117.2227 116.5188
C1-C2-O11 117.8040 117.7944 117.5811
C3-C2-O11 124.9852 124.9829 125.9002
C2-C3-C4 122.6954 122.6794 123.2733
C2-C3-H7 118.6523 118.6602 118.3624
C4-C3-H7 118.6524 118.6600 118.3643
C3-C4-C5 117.208 117.2200 116.5170
C3-C4-O10 124.9867 124.9843 125.9013
C5-C4-O10 117.8053 117.7957 117.5817
C4-C5-C6 121.5703 121.5647 122.0527
C4-C5-H8 116.6533 116.6583 116.2981
C6-C5-H8 121.7764 121.7770 121.6492
C1-C6-C5 119.7461 119.7495 119.5860
C1-C6-H9 120.1283 120.1266 120.2078
C5-C6-H9 120.1256 120.1240 120.2062
Table 5. Calculated Atomic Charges and spin densities of 1, 3-BSQ

Atomic Charge Atomic Spin Densities

Atom UB3LYP/ UB3LYP/ UB3LYP/ UB3LYP/ UB3LYP/ UB3LYP/
6-31+G 6-31++G EPR-II 6-31+G 6-31++G EPR-II
C1 0.238662 0.475939 -0.158874 0.607109 0.595648 0.527245
C2 -0.378710 -0.849469 0.255124 -0.110493 -0.083172 -0.041559
C3 0.273656 0.707708 -0.394382 -0.040621 -0.062009 -0.032179
C4 -0.378503 -0.849159 0.255088 -0.110495 -0.083167 -0.041572
C5 0.238522 0.475677 -0.158860 0.607148 0.595678 0.527274
C6 -0.310749 -0.501161 -0.127648 -0.273348 -0.265256 -0.185079
H7 0.150954 0.201447 0.101578 -0.000848 -0.000501 0.000009
H8 0.157818 0.200738 0.097908 -0.027557 -0.034601 -0.027117
H9 0.148743 0.178869 0.068617 0.007293 0.007106 0.007635
O10 -0.649140 -0.620708 -0.518245 0.183783 0.182382 0.146230
O11 -0.649102 -0.620665 -0.518213 0.183889 0.182488 0.146228
H12 0.157849 0.200785 0.097909 -0.027555 -0.034596 -0.027116

Table 6. Calculated hyperfine coupling constants of 1, 3-BSQ radical in gas-phase with C S

symmetry using different basis sets in Gauss.

UB3LYP/ UB3LYP/ UB3LYP/

6-31+g 6-31++g EPR-II
Energy
-381.4240 -381.4250 -381.5690
(Hartree)
<S2> 0.7818/0.7505 0.7818/ 0.7505 0.7824/0.7504
Dipole moment
5.6684 5.6682 4.9637
(debey)
C1 30.54882 30.62663 16.17945
C2 -8.37565 -8.38122 -6.98334
C3 -2.39168 -2.40807 -1.94995
C4 -8.37519 -8.38076 -6.98394
C5 30.55032 30.62818 16.18090
C6 -17.20433 -17.21113 -13.82268
H7 0.18492 0.18646 -0.02924
H8 -13.45468 -13.40247 -12.32391
H9 3.89831 3.87821 3.36827
O10 -8.46325 -8.46410 -3.65229
O11 -8.46804 -8.46890 -3.65243
H12 -13.45447 -13.40226 -12.32333
Table 7. Calculated bond lengths and angles of 1, 4-BSQ radical in its free form, on D 2h
symmetry (bond lengths in Å and angles in degrees)

Geometrical UB3LYP/ UB3LYP/ UB3LYP/

parameter 6-31+G 6-31++G EPR-II
C1-C2 1.4477 1.4477 1.4596
C1-C6 1.4477 1.4477 1.4596
C1-O12 1.3039 1.3041 1.2711
C2-C3 1.3785 1.3785 1.3802
C2-H7 1.0880 1.0880 1.0899
C3-C4 1.4477 1.4477 1.4596
C3-H8 1.0880 1.0880 1.0899
C4-C5 1.4477 1.4477 1.4596
C4-O11 1.3039 1.3041 1.2711
C5-C6 1.3785 1.3785 1.3802
C5-H9 1.0880 1.0880 1.0899
C6-H10 1.0880 1.0880 1.0899
C2-C1-C6 115.8589 115.8701 114.8547
C2-C1-O12 122.0705 122.0650 122.5726
C6-C1-O12 122.0705 122.0650 122.5726
C1-C2-C3 122.0705 122.0650 122.5726
C1-C2-H7 116.7761 116.7785 116.4163
C3-C2-H7 121.1534 121.1566 121.0111
C2-C3-C4 122.0705 122.0650 122.5726
C2-C3-C8 121.1534 121.1566 121.0111
C4-C3-C8 116.7761 116.7785 116.4163
C3-C4-C5 115.8589 115.8701 114.8547
C3-C4-O11 122.0705 122.0650 122.5726
C5-C4-O11 122.0705 122.0650 122.5726
C4-C5-C6 122.0705 122.0650 122.5726
C4-C5-H9 116.7761 116.7785 116.4163
C6-C5-H9 121.1534 121.1566 121.0111
C1-C6-C5 122.0705 122.0650 122.5726
C1-C6-H10 116.7761 116.7785 116.4163
C5-C6-H10 121.1534 121.1566 121.0111
Table 8. Calculated Atomic Charges and spin densities of 1, 4-BSQ

Atomic Charge Atomic Spin Densities

Atom UB3LYP/ UB3LYP/ UB3LYP/ UB3LYP/ UB3LYP/ UB3LYP/
6-31+G 6-31++G EPR-II 6-31+G 6-31++G EPR-II
C1 -0.256796 -0.650424 0.198404 0.059305 0.067318 0.073390
C2 0.044908 0.184360 -0.188437 0.076278 0.074166 0.855266
C3 0.044908 0.184360 -0.188437 0.076278 0.074166 0.855266
C4 -0.256796 -0.650424 0.198404 0.059305 0.067318 0.073390
C5 0.044908 0.184360 -0.188437 0.076278 0.074166 0.085266
C6 0.044908 0.184360 -0.188437 0.076278 0.074166 0.085266
H7 0.151586 0.194493 0.086392 -0.004812 -0.006553 -0.005465
H8 0.151586 0.194493 0.086392 -0.004812 -0.006553 -0.005465
H9 0.151586 0.194493 0.086392 -0.004812 -0.006553 -0.005465
H10 0.151586 0.194493 0.086392 -0.004812 -0.006553 -0.005465
O11 -0.636192 -0.607282 -0.494314 0.297762 0.297456 0.267008
O12 -0.636192 -0.607282 -0.494314 0.297762 0.297456 0.267008

Table 9. Calculated hyperfine coupling constants of 1, 4-BSQ radical in gas-phase with D 2h

symmetry using different basis sets in Gauss.

UB3LYP/ UB3LYP/ UB3LYP/

6-31+g 6-31++g EPR-II
Energy
-381.4500 -381.4490 -381.5940
(Hartree)
<S2> 0.7729/0.7501 0.7729/ 0.7501 0.7742/0.7500
Dipole moment
0.0000 0.0000 0.0000
(debey)
C1 -0.04608 -0.04476 -3.58945
C2 2.42200 2.43359 -0.16841
C3 2.42200 2.43359 -0.16841
C4 0.04608 -0.04476 -3.58945
C5 2.42200 2.43359 -0.16841
C6 2.42200 2.43359 -0.16841
H7 -2.39359 -2.38314 -2.39378
H8 -2.39359 -2.38314 -2.39378
H9 -2.39359 -2.38314 -2.39378
H10 -2.39359 -2.38314 -2.39378
O11 -14.83732 -14.83191 -7.69507
O12 -14.83732 -14.83191 -7.69507
Table 10. Calculated Atomic Charge and Spin Density of 1,2-BSQ in water.

Atomic Charge Atomic Spin Densities

Atom UB3LYP/ UB3LYP/
EPR-II EPR-II
C1   -0.240007   0.049769
C2   0.134785   0.105487
C3   0.134785   0.105487
C4   -0.240007   0.049769
C5   -0.155381   0.110888
C6   -0.155381   0.110888
H7   0.139870   -0.003634
H8   0.139870   -0.003634
H9   0.139870   -0.003634
H10   0.139870   -0.003634
O11   -0.516591   0.244096
O12   -0.516591      0.244096  

Table 11. Calculated Atomic Charge and Spin Density of 1,3-BSQ in water.

Atomic Charge Atomic Spin Densities

Ato
UB3LYP/ UB3LYP/
m
EPR-II EPR-II
C1   -0.177580   0.509575
C2   0.249956   -0.020010
C3   -0.428920   -0.031739
C4   0.249967   -0.020005
C5   -0.177593   0.509568
C6   -0.136977   -0.183601
H7   0.134945   -0.000057
H8   0.155672   -0.025521
H9   0.147732   0.007269
O10   -0.586429   0.140036
O11   -0.586441   0.140036
H12   0.155668     -0.025522
Table 12. Calculated Atomic Charge and Spin Density of 1,4-BSQ in water.

Atomic Charge Atomic Spin Densities

Ato
UB3LYP/ UB3LYP/
m
EPR-II EPR-II
C1   0.180871   0.104039
C2   -0.207433   0.079601
C3   -0.207433   0.079601
C4   0.180871   0.104039
C5   -0.207433   0.079601
C6   -0.207433   0.079601
H7   0.140321   -0.005084
H8   0.140321   -0.005084
H9   0.140321   -0.005084
H10   0.140321   -0.005084
O11   -0.546648   0.246927
O12   -0.546648     0.246927

0.3

0.25

0.2

0.15
Gas-phase
Solvated (water)
0.1

0.05

0
C1 C2 C3 C4 C5 C6 H7 H8 H9 H10 O11 O12

-0.05

Fig.4. Mulliken Spin densities of atoms in 1,2-BSQ in gas phase and solvated (water)
 0.6

0.5

0.4

0.3

0.2
Solvated (water)
Gas-phase
0.1

0
C1 C2 C3 C4 C5 C6 H7 H8 H9 O10 O11 H12
-0.1

-0.2

-0.3

Fig.5. Mulliken Spin densities of atoms in 1,3-BSQ in gas phase and solvated (water)

0.8

0.6

Gas-phase
0.4 Solvated (water)

0.2

0
C1 C2 C3 C4 C5 C6 H7 H8 H9 H10 O11 O12

-0.2

Fig.6. Mulliken Spin densities of atoms in 1,4-BSQ in gas phase and solvated (water)