The Blue-Violet Color of Pentamethylbismuth: A Visible Spin-Orbit Effect.
Two-component relativistic time-dependent density functional theory calculations with spin-orbit coupling predict yellow and orange-red absorption for BiPh5and BiMe5, respectively, providing an excellent explanation for their respective violet and blue-violet colors. According to the calculations, the visible absorption is clearly attributable to a single transition from a ligand-based HOMO to a low-energy LUMO with a significant contribution from a relativistically stabilized Bi 6s orbital. Surprisingly, scalar releativistic calculations completely fail to reproduce the observed visible absorption and place it at the violet/near-UV borderline instead.
Department of Chemistry University of the Free State 9300 Bloemfontein Republic of South Africa.
Jeanet
0000-0002-8120-6830
J
Conradie
Department of Chemistry UiT-The Arctic University of Norway 9037 Tromsø Norway.
Abhik
0000-0003-1161-6364
A
Ghosh
density functional calculations; pentamethylbismuth; pentaphenylbismuth; relativistic; spin-orbit effects