4.3 Catalytic Chemistry
187
+
+CO 2
+H +
−OH −
−CO
a-60
+
Energy (eV)
a-3
+CO 2
+H +
+e −
a-40
+H +
+e −
a-50
+e −
a-70
+OH −
a-4
+OH −
+CO
a-4
+CO 2
+H +
+e −
(+0.047)
(+0.320)
(-11.200)
(-16.974)
(-9.205)
(+5.006)
(-7.370)
+
+e −
Fig. 4.45 A series of relative energy changes in the Ru-COO cycle. See Fig. 4.41(a–1) as to setting
of the zero energy
(a)
(b)
Wavelength (nm)
Fig. 4.46 a Molecular structure of N3-polyene and b the calculated optical spectrum
Table 4.7 Major peaks of the calculated optical absorption spectrum of N3-polyene
No of excitation Wavelength of the
peak(in nm)
Corresponding MO
transition in TD-DFT
Coefficient of the
MO transition
Oscillator
strength
19th
598.91
HOMO → LUMO +
2
0.5157
1.9269
HOMO-5 → LUMO
0.4018
20th
595.71
HOMO → LUMO +
2
−0.3085
0.7083
HOMO-5 → LUMO
0.5433
22nd
592.69
HOMO-1 → LUMO
+ 5
0.5176
0.8305
m i j
x
=
√
2
all AO
s
r
c
i
r c
j
r ¯
x rr + 2
all AO
s
r >s
c
i
r c
j
s ¯
x rs
(4.9)
187
+
+CO 2
+H +
−OH −
−CO
a-60
+
Energy (eV)
a-3
+CO 2
+H +
+e −
a-40
+H +
+e −
a-50
+e −
a-70
+OH −
a-4
+OH −
+CO
a-4
+CO 2
+H +
+e −
(+0.047)
(+0.320)
(-11.200)
(-16.974)
(-9.205)
(+5.006)
(-7.370)
+
+e −
Fig. 4.45 A series of relative energy changes in the Ru-COO cycle. See Fig. 4.41(a–1) as to setting
of the zero energy
(a)
(b)
Wavelength (nm)
Fig. 4.46 a Molecular structure of N3-polyene and b the calculated optical spectrum
Table 4.7 Major peaks of the calculated optical absorption spectrum of N3-polyene
No of excitation Wavelength of the
peak(in nm)
Corresponding MO
transition in TD-DFT
Coefficient of the
MO transition
Oscillator
strength
19th
598.91
HOMO → LUMO +
2
0.5157
1.9269
HOMO-5 → LUMO
0.4018
20th
595.71
HOMO → LUMO +
2
−0.3085
0.7083
HOMO-5 → LUMO
0.5433
22nd
592.69
HOMO-1 → LUMO
+ 5
0.5176
0.8305
m i j
x
=
√
2
all AO
s
r
c
i
r c
j
r ¯
x rr + 2
all AO
s
r >s
c
i
r c
j
s ¯
x rs
(4.9)