Open AccessThe Blue–Violet Color of Pentamethylbismuth: A Visible Spin‐Orbit Effect
Author(s) -
Conradie Jeanet,
Ghosh Abhik
Publication year - 2017
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201600131
Subject(s) - absorption (acoustics) , homo/lumo , ultra violet , spin–orbit interaction , scalar (mathematics) , visible spectrum , blueshift , absorption spectroscopy , spin (aerodynamics) , photochemistry , physics , chemistry , optics , optoelectronics , condensed matter physics , molecule , quantum mechanics , mathematics , geometry , photoluminescence , thermodynamics
Two‐component relativistic time‐dependent density functional theory calculations with spin‐orbit coupling predict yellow and orange–red absorption for BiPh 5 and BiMe 5 , 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.