Compound-tunable embedding potential method to model local electronic excitations on f-element ions in solids: Pilot relativistic coupled cluster study of Ce and Th impurities in yttrium orthophosphate, YPO₄

Oleynichenko, A.V.; Lomachuk, Y.V.; Maltsev, D.A.; Mosyagin, N.S.; Shakhova, V.M.; Zaitsevskii, A.; Titov, A.V.

Авторы: Oleynichenko A.V., Lomachuk Y.V., Maltsev D.A., Mosyagin N.S., Shakhova V.M., Zaitsevskii A., Titov A.V.
Журнал: Physical Review B
Том: 109
Номер: 12
Год издания: 2024
Издательство: American Physical Society
Местоположение издательства: United States
Первая страница: 125106
DOI: 10.1103/PhysRevB.109.125106
Аннотация: A method to simulate local properties and processes in crystals with impurities via constructing cluster models within the frame of the compound-tunable embedding potential (CTEP) and highly-accurate {\it ab initio} relativistic molecular-type electronic structure calculations is developed and applied to the Ce and Th-doped yttrium orthophosphate crystals, YPO4, having xenotime structure. Two embedded cluster models are considered, the "minimal" one, YO8@CTEPmin, consisting of the central Y3+ cation and its first coordination sphere of eight O2− anions (i.~e.\ with broken P--O bonds), and its extended counterpart, Y(PO4)6@CTEPext, implying the full treatment of all atoms of the PO3−4 anions nearest to the central Y3+ cation. CTEPmin,ext denote here the corresponding cluster environment described within the CTEP method. The relativistic Fock-space coupled cluster (FS RCC) theory is applied to the minimal cluster model to study electronic excitations localized on Ce3+ and Th3+ impurity ions. Calculated transition energies for the cerium-doped xenotime are in a good agreement with the available experimental data (mean absolute deviation of ca.0.3 eV for 4f→5d type transitions). For the thorium-doped crystal the picture of electronic states is predicted to be quite complicated, the ground state is expected to be of the 6d character. The uncertainty for the excitation energies of thorium-doped xenotime is estimated to be within 0.35 eV. Radiative lifetimes of excited states are calculated at the FS RCC level for both doped crystals. The calculated lifetime of the lowest 5d state of Ce3+ differs from the experimentally measured one by no more than twice.
Добавил в систему: Олейниченко Александр Витальевич

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Compound-tunable embedding potential method to model local electronic excitations on f-element ions in solids: Pilot relativistic coupled cluster study of Ce and Th impurities in yttrium orthophosphate, YPO₄статья Исследовательская статья

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