The experimental absorption spectrum of fac-[Ir (ppy) 3 ] 1 has been recorded in
various media such as neat film, THF, toluene, and CH 2 Cl 2 [112]. Whatever the
medium, the absorption starts at about 17,500 cm
À1 and is characterized by several
shoulders at 20,410, 21,740, and 24,390 cm
À1 , one peak at 26,315 cm
À1 , a shoulder
at 28,170 cm
À1 , and two intense bands centered at 34,840 and 40,820 cm
À1 ,
respectively. This insensitivity to the media as well as the small effect on the
optimized geometry of fac-[Ir (ppy) 3 ] [80] justifies the neglect of solvent corrections in the theoretical approach.
The TD-DFT absorption spectrum of fac-[Ir (ppy) 3 ] 1 depicted in Fig. 1 has been
assigned on the basis of the spin-orbit states and the emissive properties of the
complexes have been interpreted from the singlet/triplet mixing and spin-orbit
splitting of the lowest S n singlet and T n triplet states (Tables 1 and 2).
The theoretical absorption spectrum obtained in vacuum starts at about
17,360 cm
À1 (Fig. 1) with states of low intensity not reported in Table 1 and is
Table 1 TD-DFT/PW91 “spin-free” states (in cm
À1
) of fac-[Ir (ppy) 3 ] 1 and associated oscillator
strengths (adapted from Brahim and Daniel [80])
State
Label
Character
Transition
energy in cm
À1
Transition
energy in eV
f
a
1
A
S 2
MLCT
18,560
2.32
7 Â 10
À3
1
E
S 5
MLCT
20,720
2.59
0.015
1
E
S 7
MLCT
21,760
2.72
0.041
3
E
T 5
MLCT
22,080
2.76
1
E
S 8
MLCT
22,720
2.84
0.013
1
A
S 9
MLCT
23,280
2.91
0.033
3
E
T 7
LC
27,440
3.43
3
E
T 12
LC/MLCT
29,920
3.74
1
A
S 12
LC
30,000
3.75
0.042
1
A
S 17
LC
32,240
4.03
2 Â 10
À3
1
A
S 18
LC/MLCT
32,560
4.07
0.05
1
E
S 21
LC/MLCT
33,280
4.16
0.040
1
A
S 22
MLCT
33,440
4.18
0.046
1
E
S 23
LC/MLCT
33,520
4.19
0.015
1
A
S 24
MLCT
33,600
4.20
0.106
1
E
S 33
MLCT
36,720
4.59
0.075
1
A
S 34
MLCT
37,040
4.63
0.083
1
A
S 35
MLCT
37,280
4.66
5 Â 10
À3
3
A
T 34
LC/MLCT
37,360
4.67
3
A
T 36
LC
37,520
4.69
1
A
S 36
LC/MLCT
37,600
4.70
0.012
1
A
S 44
LC
39,520
4.94
0.109
3
E
T 43
MLCT
39,920
4.99
1
E
S 45
LC
40,000
5.00
0.023
a
Only the “spin-free” states of interest entering in the composition of the “spin-orbit” states
described in Table 2 are reported
Absorption Spectroscopy, Emissive Properties, and Ultrafast Intersystem. . .
387
various media such as neat film, THF, toluene, and CH 2 Cl 2 [112]. Whatever the
medium, the absorption starts at about 17,500 cm
À1 and is characterized by several
shoulders at 20,410, 21,740, and 24,390 cm
À1 , one peak at 26,315 cm
À1 , a shoulder
at 28,170 cm
À1 , and two intense bands centered at 34,840 and 40,820 cm
À1 ,
respectively. This insensitivity to the media as well as the small effect on the
optimized geometry of fac-[Ir (ppy) 3 ] [80] justifies the neglect of solvent corrections in the theoretical approach.
The TD-DFT absorption spectrum of fac-[Ir (ppy) 3 ] 1 depicted in Fig. 1 has been
assigned on the basis of the spin-orbit states and the emissive properties of the
complexes have been interpreted from the singlet/triplet mixing and spin-orbit
splitting of the lowest S n singlet and T n triplet states (Tables 1 and 2).
The theoretical absorption spectrum obtained in vacuum starts at about
17,360 cm
À1 (Fig. 1) with states of low intensity not reported in Table 1 and is
Table 1 TD-DFT/PW91 “spin-free” states (in cm
À1
) of fac-[Ir (ppy) 3 ] 1 and associated oscillator
strengths (adapted from Brahim and Daniel [80])
State
Label
Character
Transition
energy in cm
À1
Transition
energy in eV
f
a
1
A
S 2
MLCT
18,560
2.32
7 Â 10
À3
1
E
S 5
MLCT
20,720
2.59
0.015
1
E
S 7
MLCT
21,760
2.72
0.041
3
E
T 5
MLCT
22,080
2.76
1
E
S 8
MLCT
22,720
2.84
0.013
1
A
S 9
MLCT
23,280
2.91
0.033
3
E
T 7
LC
27,440
3.43
3
E
T 12
LC/MLCT
29,920
3.74
1
A
S 12
LC
30,000
3.75
0.042
1
A
S 17
LC
32,240
4.03
2 Â 10
À3
1
A
S 18
LC/MLCT
32,560
4.07
0.05
1
E
S 21
LC/MLCT
33,280
4.16
0.040
1
A
S 22
MLCT
33,440
4.18
0.046
1
E
S 23
LC/MLCT
33,520
4.19
0.015
1
A
S 24
MLCT
33,600
4.20
0.106
1
E
S 33
MLCT
36,720
4.59
0.075
1
A
S 34
MLCT
37,040
4.63
0.083
1
A
S 35
MLCT
37,280
4.66
5 Â 10
À3
3
A
T 34
LC/MLCT
37,360
4.67
3
A
T 36
LC
37,520
4.69
1
A
S 36
LC/MLCT
37,600
4.70
0.012
1
A
S 44
LC
39,520
4.94
0.109
3
E
T 43
MLCT
39,920
4.99
1
E
S 45
LC
40,000
5.00
0.023
a
Only the “spin-free” states of interest entering in the composition of the “spin-orbit” states
described in Table 2 are reported
Absorption Spectroscopy, Emissive Properties, and Ultrafast Intersystem. . .
387