In this computational study, we illustrate a method for computing phosphorescence and circularly polarized phosphorescence spectra of molecular systems, which takes into account vibronic effects including both Franck-Condon and Herzberg-Teller contributions. The singlet and triplet states involved in the phosphorescent emission are described within the harmonic approximation, and the method fully takes mode-mixing effects into account when evaluating Franck-Condon integrals. Spin-orbit couplings, which are responsible for these otherwise forbidden phenomena, are accounted for by means of a relativistic two-component time-dependent density functional theory method. The model is applied to two types of chiral systems: camphorquinone, a rigid organic system that allows for an extensive benchmark, and some members of a class of iridium complexes. The merits and shortcomings of the methods are discussed, and some perspectives for future developments are offered.
|Titolo:||Computational simulation of vibrationally resolved spectra for spin-forbidden transitions|
|Data di pubblicazione:||2018|
|Parole Chiave:||camphorquinone; circularly polarized phosphorescence; iridium complexes; phosphorescence; vibronic spectroscopy; Analytical Chemistry; Catalysis; Pharmacology; Drug Discovery3003 Pharmaceutical Science; Spectroscopy; Organic Chemistry|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1002/chir.22864|
|Appare nelle tipologie:||1.1 Articolo in rivista|