58
2 Actual Potentials of Theoretical Chemistry: What Can Be Obtained
Fig. 2.51 Molecular
structure of heterofluorene:
M = B, Al, Ga, or In.
Reproduced from
Matsumoto et al. (2015) with
permission from the Royal
Society of Chemistry
M
t
Bu
Me 2 N
t
Bu
with the calculated results of phosphorescence (Matsumoto et al. 2015). Theoretical
calculations with the DFT/B3LYP/6-31G** for B-, Al-, and Ga-fluorenes, and with
the DFT/B3LYP/LANL2DZ for Ga- and In-fluorenes were performed for the structural optimization at the S 0 state and TD-DFT/UB3LYP with the same bases at the T 1
state. The calculated phosphorescence for Ga- and In-fluorenes were at 523.13 and
525.87 nm, respectively, comparable with the experimental data in Table 2.15. In the
description of phosphorescence, it is essential to estimate the total wavefunction of
the T 1 state with mixing of the S 0 -state wavefunction through the spin-orbit coupling
interaction with the coefficient α as
Φ Total = Ψ T 1 + αΨ S 0
(2.42)
The calculated α is listed in Table 2.15 as well. Thus the phosphorescent behavior
can also be estimated by theoretical calculation.
2.5.3 Circular Dichroism (CD) Spectrum
In organic chemistry field, it is well known that molecules having asymmetric carbon
(or Si, Ge) is optically active. These optically active or chiral molecules cause optical
spectroscopic effects such as optical rotation, optical rotatory dispersion, and circular
dichroism (CD) by using circularly polarized light. These phenomena take place by
difference between optical absorptions of chiral molecules obtained by left-hand
2 Actual Potentials of Theoretical Chemistry: What Can Be Obtained
Fig. 2.51 Molecular
structure of heterofluorene:
M = B, Al, Ga, or In.
Reproduced from
Matsumoto et al. (2015) with
permission from the Royal
Society of Chemistry
M
t
Bu
Me 2 N
t
Bu
with the calculated results of phosphorescence (Matsumoto et al. 2015). Theoretical
calculations with the DFT/B3LYP/6-31G** for B-, Al-, and Ga-fluorenes, and with
the DFT/B3LYP/LANL2DZ for Ga- and In-fluorenes were performed for the structural optimization at the S 0 state and TD-DFT/UB3LYP with the same bases at the T 1
state. The calculated phosphorescence for Ga- and In-fluorenes were at 523.13 and
525.87 nm, respectively, comparable with the experimental data in Table 2.15. In the
description of phosphorescence, it is essential to estimate the total wavefunction of
the T 1 state with mixing of the S 0 -state wavefunction through the spin-orbit coupling
interaction with the coefficient α as
Φ Total = Ψ T 1 + αΨ S 0
(2.42)
The calculated α is listed in Table 2.15 as well. Thus the phosphorescent behavior
can also be estimated by theoretical calculation.
2.5.3 Circular Dichroism (CD) Spectrum
In organic chemistry field, it is well known that molecules having asymmetric carbon
(or Si, Ge) is optically active. These optically active or chiral molecules cause optical
spectroscopic effects such as optical rotation, optical rotatory dispersion, and circular
dichroism (CD) by using circularly polarized light. These phenomena take place by
difference between optical absorptions of chiral molecules obtained by left-hand