caa a22 4500 605487685 CHVBK 20210128100451.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s00214-015-1639-1 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1639-1 Structural relaxation effects on the lowest $$4f{-}5d$$ 4 f - 5 d transition of $$\hbox {Ce}^{3+}$$ Ce 3 + in garnets [Elektronische Daten] [Quan Phung, Zoila Barandiarán, Luis Seijo] The role of structural relaxations on the energy of the lowest $$4f{-}5d$$ 4 f - 5 d transition of $$\hbox {Ce}^{3+}$$ Ce 3 + in garnets is studied by means of ab initio calculations. This study completes previous studies on the roles of the interactions of the Cerium impurity with its first neighbors and with the rest of the solid hosts, before the relaxations take place. Periodic boundary conditions density functional theory calculations (DFT) and second-order perturbation theory spin-orbit coupling embedded-cluster wave function theory calculations (WFT) have been performed in the garnets $$\hbox {Y}_{3}\hbox {Al}_{5}\hbox {O}_{12}$$ Y 3 Al 5 O 12 , $$\hbox {Lu}_{3}\hbox {Al}_{5}\hbox {O}_{12}$$ Lu 3 Al 5 O 12 , $$\hbox {Y}_{3}\hbox {Ga}_{5}\hbox {O}_{12}$$ Y 3 Ga 5 O 12 , $$\hbox {Lu}_{3}\hbox {Ga}_{5}\hbox {O}_{12}$$ Lu 3 Ga 5 O 12 , and $$\hbox {Ca}_{3}\hbox {Sc}_{2}\hbox {Si}_{3}\hbox {O}_{12}$$ Ca 3 Sc 2 Si 3 O 12 doped with $$\hbox {Ce}^{3+}$$ Ce 3 + . The local relaxation effects on the $$4f{-}5d$$ 4 f - 5 d transition are similar in the WFT and DFT calculations. They produce a blue shift in Al and Ga garnets in which Ce substitutes for smaller Y and Lu cations, which is found to be basically due to the local expansions around the impurity, with only minor contributions from angular relaxations. Atomic relaxations of more distant neighbors enhance the blue shift. Although the embedding effects of the undistorted garnets are known to make the differences between the $$4f{-}5d$$ 4 f - 5 d transition in Al and Ga garnets, we find that the structural relaxations are responsible for the small differences between the $$4f{-}5d$$ 4 f - 5 d transition in $$\hbox {Y}_{3}\hbox {Al}_{5}\hbox {O}_{12}$$ Y 3 Al 5 O 12 : $$\hbox {Ce}^{3+}$$ Ce 3 + and $$\hbox {Lu}_{3}\hbox {Al}_{5}\hbox {O}_{12}$$ Lu 3 Al 5 O 12 : $$\hbox {Ce}^{3+}$$ Ce 3 + , and in $$\hbox {Y}_{3}\hbox {Ga}_{5}\hbox {O}_{12}$$ Y 3 Ga 5 O 12 : $$\hbox {Ce}^{3+}$$ Ce 3 + and $$\hbox {Lu}_{3}\hbox {Ga}_{5}\hbox{O}_{12}$$ Lu 3 Ga 5 O 12 : $$\hbox {Ce}^{3+}$$ Ce 3 + . Springer-Verlag Berlin Heidelberg, 2015 Ce nationallicence YAG nationallicence Garnets nationallicence $$4f{-}5d$$ 4 f - 5 d transitions nationallicence Ab initio nationallicence Defect nationallicence Relaxation nationallicence Phung Quan Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001, Leuven, Belgium aut Barandiarán Zoila Departamento de Química, Universidad Autónoma de Madrid, 28049, Madrid, Spain aut Seijo Luis Departamento de Química, Universidad Autónoma de Madrid, 28049, Madrid, Spain aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-9 1432-881X 134:3<1 2015 134 214 https://doi.org/10.1007/s00214-015-1639-1 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1639-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Phung Quan Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001, Leuven, Belgium aut NATIONALLICENCE 700 1- Barandiarán Zoila Departamento de Química, Universidad Autónoma de Madrid, 28049, Madrid, Spain aut NATIONALLICENCE 700 1- Seijo Luis Departamento de Química, Universidad Autónoma de Madrid, 28049, Madrid, Spain aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-9 1432-881X 134:3<1 2015 134 214