Structural and Thermodynamic Stability of the "1111" Structure Type: A Case Study of the EuFZnPn Series

Igor V Plokhikh; Dmitri O Charkin; Valeriy Yu Verchenko; Alexey N Kuznetsov; Sergey M Kazakov; Alexander A Tsirlin; Andrei V Shevelkov

doi:10.1021/acs.inorgchem.6b02297

Structural and Thermodynamic Stability of the "1111" Structure Type: A Case Study of the EuFZnPn Series

Inorg Chem. 2016 Dec 5;55(23):12409-12418. doi: 10.1021/acs.inorgchem.6b02297. Epub 2016 Nov 21.

Authors

Igor V Plokhikh¹, Dmitri O Charkin¹, Valeriy Yu Verchenko^{1

2}, Alexey N Kuznetsov^{1

3}, Sergey M Kazakov¹, Alexander A Tsirlin⁴, Andrei V Shevelkov¹

Affiliations

¹ Department of Chemistry, Lomonosov Moscow State University , 119991 Moscow, Russia.
² National Institute of Chemical Physics and Biophysics , 12618 Tallinn, Estonia.
³ N.S. Kurnakov Institute of General and Inorganic Chemistry RAS , 119991 Moscow, Russia.
⁴ Experimental Physics VI, Center for Correlations and Magnetism, Institute of Physics, University of Augsburg , 86135 Augsburg, Germany.

PMID: 27934435
DOI: 10.1021/acs.inorgchem.6b02297

Abstract

Two new compounds with the LaOAgS structure, EuFZnAs (1) and EuFZnSb (2), were obtained via solid state reaction. Both compounds are tetragonal (P4/nmm) with the cell parameters a = 4.1000(1) Å and c = 9.0811(1) Å for 1 and a = 4.2852(1)Å and c = 9.4238(1)Å for 2. The absence of their phosphide analog can be explained based on crystal chemical considerations as well as on quantum-chemical estimates of their thermodynamic stability with respect to EuF₂ and EuZn₂Pn₂. The magnetic response of 1 and 2 is ascribed to the presence of Eu²⁺ ions. Both compounds are paramagnetic down to low temperatures, where they order antiferromagnetically at ∼5 K and ∼3 K, respectively. They are narrow-gap semiconductors, and EuFZnSb demonstrates a relatively high value of the Seebeck coefficient.