New and refined bond valence parameters for Te4+–F−, Te4+–S2− and Te4+–Se2− ion pairs

David Hamani; Lyna Torzuoli; Assil Bouzid; Philippe Thomas; Olivier Masson

doi:10.1515/zkri-2022-0042

Published by De Gruyter (O) September 19, 2022

New and refined bond valence parameters for Te⁴⁺–F⁻, Te⁴⁺–S²⁻ and Te⁴⁺–Se²⁻ ion pairs

David Hamani , Lyna Torzuoli , Assil Bouzid , Philippe Thomas and Olivier Masson

From the journal Zeitschrift für Kristallographie - Crystalline Materials

https://doi.org/10.1515/zkri-2022-0042

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Abstract

New and refined bond valence parameters related to ion pairs constituted of the tellurium Te⁴⁺ cation and non-oxide Xⁿ⁻ anions (X = F, S or Se) are proposed. After a selection of specific crystalline structures, the optimization of the bond valence parameters R and b with a cutoff distance is carried out by minimizing the root mean square deviation of the Te⁴⁺ cation valence. The results are R = 1.728 Å and b = 0.622 Å with cutoff = 5.3 Å for the Te⁴⁺–F⁻ pair and R = 2.444 Å and b = 0.387 Å with cutoff = 4.5 Å for the Te⁴⁺–S²⁻ pair. These parameters lead to a lower dispersion of the calculated valences around the formal valence compared to that obtained with the parameters available in the literature. As for the new set related to the Te⁴⁺–Se²⁻ pair, we find R = 2.578 Å and b = 0.296 Å with cutoff = 3.7 Å.

Keywords: bond valence parameters; non-oxide anions; tellurium Te(IV)

Corresponding author: David Hamani, Centre Européen de la Céramique, Institut de Recherche sur les Céramiques (IRCER) – UMR CNRS 7315, Université de Limoges, 12 rue Atlantis, 87068 Limoges Cedex, France, E-mail: david.hamani@unilim.fr

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

Appendix

Comparison of the F⁻, S²⁻ and Se²⁻ valences obtained from different bond valence parameter sets for structures containing one anion type (11 structures containing F⁻, 6 structures containing S²⁻ and 4 structures containing Se²⁻).

ICSD #	Structure	Non-equivalent F⁻ position #	F⁻ valence (v.u.)
ICSD #	Structure	Non-equivalent F⁻ position #	Brese & O’Keeffe [19]	This work with b fixed at 0.37 Å	This work
16,108	Sb₂TeF₁₄	1	1.156	1.129	0.905
		2	1.092	1.055	0.911
		3	1.146	1.119	0.886
		4	0.972	0.968	1.102
		5	0.951	0.948	1.069
		6	0.936	0.932	1.069
		7	0.905	0.905	0.942
		8	0.888	0.887	0.987
		9	0.920	0.920	0.951
		10	1.204	1.204	1.237
		11	0.822	0.822	0.869
		12	1.008	1.008	1.051
		13	0.960	0.959	1.043
		14	0.823	0.823	0.850
81,862	BaTe₂F₁₀	1	1.021	1.005	1.046
		2	0.907	0.872	0.990
		3	1.161	1.138	1.062
		4	1.077	1.057	1.050
		5	0.963	0.940	0.985
81,865	PbTeF₆	1	0.962	0.961	1.072
		2	0.908	0.892	0.926
		3	0.961	0.944	0.951
		4	0.865	0.850	0.964
		5	0.957	0.940	1.043
		6	1.130	1.105	1.057
84,364	KTe₂F₉	1	1.188	1.163	1.029
84,364	KTeF₅	1	1.030	1.011	0.986
		2	1.159	1.133	1.020
		2	1.011	0.991	0.971
		3	1.147	1.114	1.016
		3	1.195	1.170	1.065
		4	0.993	0.974	0.956
		5	1.029	1.009	0.953
		6	0.927	0.907	1.016
		7	0.865	0.837	0.978
		8	0.943	0.923	0.965
		9	0.888	0.867	1.027
85,452	TeF₄	1	1.043	1.018	1.020
		2	0.983	0.959	0.985
		3	1.140	1.113	1.037
		4	0.897	0.875	1.050
88,416	BaTeF₆	1	1.008	0.979	0.980
		2	1.092	1.051	1.066
		3	1.097	1.062	1.068
		4	0.849	0.833	0.941
		5	0.997	0.968	1.005
		6	1.065	1.048	1.043
90,619	TlTeF₅	1	1.144	1.122	1.018
		2	1.015	0.997	0.974
		3	0.984	0.963	0.990
200,252	CsTeF₅	1	1.029	1.009	1.018
		2	1.092	1.070	0.973
		3	1.305	1.268	1.049
202,879	NaTeF₅	1	1.141	1.094	1.045
		2	1.043	1.022	0.987
		3	0.988	0.957	0.999
203,140	RbTeF₅	1	1.148	1.114	1.017
		2	0.982	0.954	0.961
		3	0.971	0.938	0.939
		4	1.123	1.089	0.976
		5	1.000	0.983	0.960
		6	0.907	0.888	0.937

ICSD #	Structure	Non-equivalent S²⁻ position #	S²⁻ valence (v.u.)
ICSD #	Structure	Non-equivalent S²⁻ position #	Brown [20]	This work with b fixed at 0.37 Å	This work
8	BaTeS₃	1	1.868	1.876	1.878
		2	1.962	1.970	1.974
85,135	Ag₂TeS₃	1	2.664	2.678	2.718
		2	2.084	2.092	2.108
		3	1.998	2.005	2.010
165,378	Cs₂MnTe₂S₆	1	1.922	1.929	1.926
415,120	Li₂TeS₃	1	2.521	2.533	2.585
		2	2.026	2.033	2.047
		3	1.974	1.982	2.003
424,890	Cs₂TeS₃	1	2.069	2.076	2.065
		2	2.044	2.051	2.042
		3	1.866	1.874	1.867
		4	1.952	1.959	1.947
		5	1.922	1.930	1.917
		6	1.775	1.782	1.777
430,311	Na₂TeS₃	1	2.007	2.015	2.016
		2	2.025	2.031	2.027
		3	2.101	2.108	2.099

ICSD #	Structure	Non-equivalent Se²⁻ position #	Se²⁻ valence (v.u.)
ICSD #	Structure	Non-equivalent Se²⁻ position #	This work with b fixed at 0.37 Å	This work
63,011	Na₂TeSe₃ (mC48)	1	2.020	2.007
		2	1.982	1.956
		3	2.122	2.158
63,012	K₂TeSe₃	1	2.143	2.175
		2	2.048	2.073
		3	1.966	1.992
415,121	Li₂TeSe₃	1	2.004	2.017
		2	2.156	2.190
		3	2.065	1.986
430,313	Na₂TeSe₃ (mP24)	1	2.003	1.975
		2	2.043	2.031
		3	2.151	2.194

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Received: 2022-07-13

Accepted: 2022-09-05

Published Online: 2022-09-19

Published in Print: 2022-11-25

New and refined bond valence parameters for Te⁴⁺–F⁻, Te⁴⁺–S²⁻ and Te⁴⁺–Se²⁻ ion pairs

Abstract

References

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