258
A. V. Pomogaeva and A. Y. Timoshkin
Fig. 6.33 PDOS of F 3 [HGaNH] 114 F 3 (a) and (CH 3 ) 3 [HGaNH] 114 (CH 3 ) 3 (b) Contributions from
Ga atoms are shown by black lines, from N atoms by blue dash-dotted lines, and from backbone
H atoms by green dashed lines, and contributions from terminal groups (F or CH 3 ) are presented
by red lines. For drawing this figure, the middle of the energy gap is chosen as the zero energy.
Reproduction of material from PCCP (Physical Chemistry Chemical Physics). (Reproduced from
Ref. [59] with permission from the PCCP Owner Societies)
In contrast, methyl substituents produce a relatively sparse spectrum of the highest
occupied molecular orbitals (Fig. 6.33b).
The values of HOMO-LUMO gaps for all considered oligomers with n = 38
are shown in Fig. 6.34. In all cases, the smallest HOMO-LUMO gap corresponds
to the oligomer with a methyl group at the Ga atom and fluorine at the nitrogen
atom. The largest values of the HOMO-LUMO gap correspond to strong electronwithdrawing substituents (F, CF 3 ) at the terminal Ga atoms and electron-donating
groups (CH 3 ) at the terminal N atoms. Thus, substituents which reduce the dipole
A. V. Pomogaeva and A. Y. Timoshkin
Fig. 6.33 PDOS of F 3 [HGaNH] 114 F 3 (a) and (CH 3 ) 3 [HGaNH] 114 (CH 3 ) 3 (b) Contributions from
Ga atoms are shown by black lines, from N atoms by blue dash-dotted lines, and from backbone
H atoms by green dashed lines, and contributions from terminal groups (F or CH 3 ) are presented
by red lines. For drawing this figure, the middle of the energy gap is chosen as the zero energy.
Reproduction of material from PCCP (Physical Chemistry Chemical Physics). (Reproduced from
Ref. [59] with permission from the PCCP Owner Societies)
In contrast, methyl substituents produce a relatively sparse spectrum of the highest
occupied molecular orbitals (Fig. 6.33b).
The values of HOMO-LUMO gaps for all considered oligomers with n = 38
are shown in Fig. 6.34. In all cases, the smallest HOMO-LUMO gap corresponds
to the oligomer with a methyl group at the Ga atom and fluorine at the nitrogen
atom. The largest values of the HOMO-LUMO gap correspond to strong electronwithdrawing substituents (F, CF 3 ) at the terminal Ga atoms and electron-donating
groups (CH 3 ) at the terminal N atoms. Thus, substituents which reduce the dipole