Computational simulation of vibrationally resolved spectra for spin‐forbidden transitions. Issue 7 (4th May 2018)

• Record Type: Journal Article
• Authors: Egidi, Franco; Fusè, Marco; Baiardi, Alberto; Bloino, Julien; Li, Xiaosong; Barone, Vincenzo
• Is Part Of: Chirality. Volume 30:Issue 7(2018)
• Page Start: 850
• Page End: 865
• Publication Date: 2018-05-04
• Subjects: camphorquinone -- circularly polarized phosphorescence -- iridium complexes -- phosphorescence -- vibronic spectroscopy; Chirality -- Periodicals; Pharmaceutical chemistry -- Periodicals; 541.22
• DOI: 10.1002/chir.22864
• Languages: English
• ISSNs: 0899-0042

Abstract

Abstract: 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. Abstract :