Quaternary Selenides EuLnCuSe3: Synthesis, Structures, Properties and In Silico Studies

Описание

Тип публикации: статья из журнала

Год издания: 2022

Идентификатор DOI: 10.3390/ijms23031503

Ключевые слова: ab initio calculations, inorganic materials, lattice dynamics, magnetic measurements, negative magnetization, optical spectroscopy, vibrational spectroscopy

Аннотация: In this work, we report on the synthesis, in-depth crystal structure studies as well as optical and magnetic properties of newly synthesized heterometallic quaternary selenides of the Eu+2Ln+3Cu+1Se3 composition. Crystal structures of the obtained compounds were refined by the derivative difference minimization (DDM) method from thПоказать полностьюe powder X-ray diffraction data. The structures are found to belong to orthorhombic space groups Pnma (structure type Ba2MnS3 for EuLaCuSe3 and structure type Eu2CuS3 for EuLnCuSe3, where Ln = Sm, Gd, Tb, Dy, Ho and Y) and Cmcm (structure type KZrCuS3 for EuLnCuSe3, where Ln = Tm, Yb and Lu). Space groups Pnma and Cmcm were delimited based on the tolerance factor t’, and vibrational spectroscopy additionally confirmed the formation of three structural types. With a decrease in the ionic radius of Ln3+ in the reported structures, the distortion of the (LnCuSe3) layers decreases, and a gradual formation of the more symmetric structure occurs in the sequence Ba2MnS3 → Eu2CuS3 → KZrCuS3. According to magnetic studies, compounds EuLnCuSe3 (Ln = Tb, Dy, Ho and Tm) each exhibit ferrimagnetic properties with transition temperatures ranging from 4.7 to 6.3 K. A negative magnetization effect is observed for compound EuHoCuSe3 at temperatures below 4.8 K. The magnetic properties of the discussed selenides and isostructural sulfides were compared. The direct optical band gaps for EuLnCuSe3, subtracted from the corresponding diffuse reflectance spectra, were found to be 1.87– 2.09 eV. Deviation between experimental and calculated band gaps is ascribed to lower d states of Eu2+ in the crystal field of EuLnCuSe3, while anomalous narrowing of the band gap of EuYbCuSe3 is explained by the low-lying charge-transfer state. Ab initio calculations of the crystal structures, elastic properties and phonon spectra of the reported compounds were performed. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.

Ссылки на полный текст

Издание

Журнал: International Journal of Molecular Sciences

Выпуск журнала: Vol. 23, Is. 3

Номера страниц: 1503

ISSN журнала: 16616596

Персоны

  • Grigoriev Maxim V. (Univ Tyumen, Lab Theory & Optimizat Chem & Technol Processes, Tyumen 625003, Russia)
  • Solovyov Leonid A. (SB RAS, Inst Chem & Chem Technol, Fed Res Ctr KSC, Krasnoyarsk 660036, Russia)
  • Ruseikina Anna V. (Univ Tyumen, Inst Chem, Tyumen 625003, Russia)
  • Aleksandrovsky Aleksandr S. (Siberian Fed Univ, Dept Photon & Laser Technol, Krasnoyarsk 660079, Russia; RAS, SB, Fed Res Ctr KSC, Kirensky Inst Phys, Krasnoyarsk 660036, Russia)
  • Chernyshev Vladimir A. (Ural Fed Univ, Inst Nat Sci & Math, Mira Str 19, Ekaterinburg 620002, Russia)
  • Velikanov Dmitriy A. (RAS, SB, Fed Res Ctr KSC, Kirensky Inst Phys, Krasnoyarsk 660036, Russia)
  • Garmonov Alexander A. (Univ Tyumen, Inst Phys & Technol, Tyumen 625003, Russia)
  • Molokeev Maxim S. (RAS, SB, Fed Res Ctr KSC, Kirensky Inst Phys, Krasnoyarsk 660036, Russia; Kemerovo State Univ, Res & Dev Dept, Kemerovo 650000, Russia; Siberian Fed Univ, Inst Engn Phys & Radioelect, Krasnoyarsk 660079, Russia)
  • Oreshonkov Aleksandr S. (RAS, SB, Fed Res Ctr KSC, Kirensky Inst Phys, Krasnoyarsk 660036, Russia; Siberian Fed Univ, Sch Engn & Construct, Krasnoyarsk 660041, Russia)
  • Shestakov Nikolay P. (RAS, SB, Fed Res Ctr KSC, Kirensky Inst Phys, Krasnoyarsk 660036, Russia)
  • Matigorov Alexey V. (Univ Tyumen, Engn Ctr Composite Mat Based Wolfram Cpds & Rare, Tyumen 625003, Russia)
  • Volkova Svetlana S. (Univ Tyumen, Inst Chem, Tyumen 625003, Russia)
  • Ostapchuk Evgeniy A. (Univ Tyumen, Lab Theory & Optimizat Chem & Technol Processes, Tyumen 625003, Russia)
  • Kertman Alexander V. (Univ Tyumen, Inst Chem, Tyumen 625003, Russia)
  • Schleid Thomas (Univ Stuttgart, Inst Inorgan Chem, D-70569 Stuttgart, Germany)
  • Safin Damir A. (Univ Tyumen, Inst Chem, Tyumen 625003, Russia; Kurgan State Univ, Adv Mat Ind & Biomed Lab, Sovetskaya Str 63-4, Kurgan 640020, Russia; Ural Fed Univ, Innovat Ctr Chem & Pharmaceut Technol, Mira Str 19, Ekaterinburg 620002, Russia)