underestimates the values of the gaps [44, 45]. However, the two methods show
similar trends.
Figure 6 shows the shapes of the HOMO and LUMO orbitals for the five lowest
energy conformers, some representative higher energy ones and the conformers of
some S/S′ symmetric pairs. The shapes indicate greater electron density and similar
distribution in the two naphthalene moieties than in the isoquinoline moieties for
Table 6 Dipole moment of the conformers of jozimine A 2 listed in Table 2, in vacuo and in the
three solvents considered. HF/6-31G(d,p) and (DFT/B3LYP/6-31+G(d,p) results, respectively
denoted as HF and DFT in the column headings. The results in vacuo are from full optimization
calculations, the results in solution are from single point PCM calculations on the
in-vacuo-optimized geometries
Conformer
Dipole moment (Debye)
HF
DFT
vac
chlrf
actn
aq
vac
chlrf
actn
aq
a-b-e-f-g-h-p-v-x
2.65
2.67
2.55
2.44
2.81
2.87
2.74
2.58
a-b-e-f-g-h-q-v-x
5.46
5.96
6.06
5.97
5.32
5.93
6.09
5.99
a-b-e-f-g-h-q-t-x
5.03
5.41
5.43
5.34
5.01
5.50
5.57
5.45
a-b-e-f-g-h-q-v-y
6.83
7.46
7.55
7.44
6.59
7.36
7.52
7.39
a-b-e-f-g-h-p-t-x
7.53
8.29
8.50
8.43
7.33
8.28
8.57
8.49
a-b-f-h-q-v-x
4.25
4.95
4.51
4.31
4.04
4.36
4.41
4.22
a-d-e-f-g-h-q-v-x
4.56
4.85
4.87
4.73
4.70
5.11
−
a
−
a
b-c-e-f-g-h-q-t-x
5.03
6.12
6.29
6.28
5.52
6.22
6.46
6.41
a-b-e-g-q-t-x
4.20
4.45
4.47
4.27
4.10
4.39
4.42
4.21
b-c-e-f-g-h-p-v-x
4.11
4.53
4.63
4.69
4.15
4.65
4.81
4.83
a-d-e-f-g-h-p-v-x
4.11
4.53
4.64
4.69
4.15
4.66
4.80
4.83
a-b-e-g-p-v-x
3.93
4.24
4.29
4.37
4.38
4.79
4.85
4.91
a-b-f-h-p-v-x
3.93
4.23
4.28
4.36
4.38
4.78
−
a
4.90
a-b-e-g-v-y
4.84
5.08
5.04
4.89
4.36
−
a
−
a
4.27
a-b-f-h-v-y
4.84
5.07
5.04
4.89
4.36
4.59
4.55
4.27
a-b-e-g-p-t-x
4.96
5.21
5.18
4.88
4.78
5.12
5.10
4.78
a-b-f-g-p-t-x
4.95
5.22
5.17
4.88
4.77
5.11
5.09
4.78
c-d-e-f-g-h-p-v-x
0.50
0.20
0.02
0.17
0.70
0.40
0.20
0.21
a-d-e-g-p-t-x
4.62
5.10
5.24
5.20
4.03
4.54
4.70
4.62
a-b-q-v-y
1.38
1.13
−
a
0.65
0.59
−
a
−
a
0.41
a-b-p-t-x
1.42
1.19
0.96
0.50
1.08
0.85
0.60
0.15
c-d-f-h-p-v-x
3.83
4.28
4.49
4.65
4.04
4.60
4.82
4.98
c-d-f-h-q-v-x
3.79
4.22
4.39
4.39
3.71
4.56
4.29
−
a
b-c-q-v-y
3.91
4.40
4.56
4.67
3.97
4.69
5.00
5.25
a-d-q-v-y
3.91
4.40
4.56
4.67
3.97
4.70
5.00
5.24
c-d-q-v-y
1.28
1.81
2.03
2.40
2.07
2.83
3.19
3.70
c-d-p-t-x
1.33
1.86
2.09
2.64
1.84
2.52
2.87
3.48
a The calculation for this conformer did not converge in the given solvent
Computational Study of Jozimine A 2 , a Naphthylisoquinoline …
319
similar trends.
Figure 6 shows the shapes of the HOMO and LUMO orbitals for the five lowest
energy conformers, some representative higher energy ones and the conformers of
some S/S′ symmetric pairs. The shapes indicate greater electron density and similar
distribution in the two naphthalene moieties than in the isoquinoline moieties for
Table 6 Dipole moment of the conformers of jozimine A 2 listed in Table 2, in vacuo and in the
three solvents considered. HF/6-31G(d,p) and (DFT/B3LYP/6-31+G(d,p) results, respectively
denoted as HF and DFT in the column headings. The results in vacuo are from full optimization
calculations, the results in solution are from single point PCM calculations on the
in-vacuo-optimized geometries
Conformer
Dipole moment (Debye)
HF
DFT
vac
chlrf
actn
aq
vac
chlrf
actn
aq
a-b-e-f-g-h-p-v-x
2.65
2.67
2.55
2.44
2.81
2.87
2.74
2.58
a-b-e-f-g-h-q-v-x
5.46
5.96
6.06
5.97
5.32
5.93
6.09
5.99
a-b-e-f-g-h-q-t-x
5.03
5.41
5.43
5.34
5.01
5.50
5.57
5.45
a-b-e-f-g-h-q-v-y
6.83
7.46
7.55
7.44
6.59
7.36
7.52
7.39
a-b-e-f-g-h-p-t-x
7.53
8.29
8.50
8.43
7.33
8.28
8.57
8.49
a-b-f-h-q-v-x
4.25
4.95
4.51
4.31
4.04
4.36
4.41
4.22
a-d-e-f-g-h-q-v-x
4.56
4.85
4.87
4.73
4.70
5.11
−
a
−
a
b-c-e-f-g-h-q-t-x
5.03
6.12
6.29
6.28
5.52
6.22
6.46
6.41
a-b-e-g-q-t-x
4.20
4.45
4.47
4.27
4.10
4.39
4.42
4.21
b-c-e-f-g-h-p-v-x
4.11
4.53
4.63
4.69
4.15
4.65
4.81
4.83
a-d-e-f-g-h-p-v-x
4.11
4.53
4.64
4.69
4.15
4.66
4.80
4.83
a-b-e-g-p-v-x
3.93
4.24
4.29
4.37
4.38
4.79
4.85
4.91
a-b-f-h-p-v-x
3.93
4.23
4.28
4.36
4.38
4.78
−
a
4.90
a-b-e-g-v-y
4.84
5.08
5.04
4.89
4.36
−
a
−
a
4.27
a-b-f-h-v-y
4.84
5.07
5.04
4.89
4.36
4.59
4.55
4.27
a-b-e-g-p-t-x
4.96
5.21
5.18
4.88
4.78
5.12
5.10
4.78
a-b-f-g-p-t-x
4.95
5.22
5.17
4.88
4.77
5.11
5.09
4.78
c-d-e-f-g-h-p-v-x
0.50
0.20
0.02
0.17
0.70
0.40
0.20
0.21
a-d-e-g-p-t-x
4.62
5.10
5.24
5.20
4.03
4.54
4.70
4.62
a-b-q-v-y
1.38
1.13
−
a
0.65
0.59
−
a
−
a
0.41
a-b-p-t-x
1.42
1.19
0.96
0.50
1.08
0.85
0.60
0.15
c-d-f-h-p-v-x
3.83
4.28
4.49
4.65
4.04
4.60
4.82
4.98
c-d-f-h-q-v-x
3.79
4.22
4.39
4.39
3.71
4.56
4.29
−
a
b-c-q-v-y
3.91
4.40
4.56
4.67
3.97
4.69
5.00
5.25
a-d-q-v-y
3.91
4.40
4.56
4.67
3.97
4.70
5.00
5.24
c-d-q-v-y
1.28
1.81
2.03
2.40
2.07
2.83
3.19
3.70
c-d-p-t-x
1.33
1.86
2.09
2.64
1.84
2.52
2.87
3.48
a The calculation for this conformer did not converge in the given solvent
Computational Study of Jozimine A 2 , a Naphthylisoquinoline …
319