Relativistic Effects in Photoluminescence and Photocatalysis of Transition Metal Systems
Xiaoyan Caoa, Michael Dolga, Weihai Fangb
aInstitute for Theoretical Chemistry, University of Cologne, Cologne, Germany
bDepartment of Chemistry, Beijing Normal University, Beijing, P.R. China
Email: x.cao@uni-koeln.de
Materials containing d and f transition metals are widely used in laser materials, OLED, catalysts, and biological imaging due to their unique optical and electronic properties. By using relativistic and non-relativistic energy consistent pseudopotentials (PPs) [1] combined with DFT and/or CASPT2/CASSCF methods we have published recently several papers [2-4] on the photochemistry of such materials. For the gold-doped silver nanoclusters, the calculations have shown that the relativistic effects mainly originating from the Au atoms enhance the fluorescence intensity, especially for highly doped Ag26Au3, Ag25Au4, and Ag24Au5; For the photoluminescence of Eu-antenna probes our studies have proven that the energy resonance crossing is controlled by an overall nonet-quintet intersystem crossing due to the spin-orbit coupling among the sublevels of the involved states; for the visible−light photocatalysis for C(sp3)−H Fluorination by uranyl, by taking into account the relativistic effects the rate constants for the hydrogen atom abstraction reaction is increased from 2.97 ×103 s−1 to 1.70 ×106 s−1.
References
- M. Dolg, X. Cao (2018), in T. P. Hanussa, W. Evans (Eds.), Encyclopedia of Inorganic and Bioinorganic Chemistry, The heaviest metals: Science and Technology of the Actinides and Beyond. DOI: 10.1002/9781119951438.eibc2540. Chichester: Wiley.
- L. Wu, X. Cao, X. Chen, W. Fang, and M. Dolg (2018), Angew. Chem., 2018, 57(36):11812
- X. Xie, P. Xiao, X. Cao, W. Fang, G. Cui, M. Dolg (2018), Angew. Chem., 2018, 57(31):9965,
- Q. Zhang, L. Wu, X. Cao, X. Chen, W. Fang, M. Dolg (2017), Angew. Chem. 56(27):7986-7990.