Computational simulation of vibrationally resolved spectra for spin‐forbidden transitions |
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| Authors: | Franco Egidi Marco Fusè Alberto Baiardi Julien Bloino Xiaosong Li Vincenzo Barone |
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| Affiliation: | 1. Scuola Normale Superiore, Pisa, Italy;2. Institute of Chemistry of Organometallic Compounds, National Research Council of Italy, Pisa, Italy;3. Department of Chemistry, University of Washington, Seattle, Washington, USA |
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| 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. |
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| Keywords: | camphorquinone circularly polarized phosphorescence iridium complexes phosphorescence vibronic spectroscopy |
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