Crystal structure and orbital-singlet state of Ag{sub x}VP{sub 2}O{sub 7}
The crystal structure and electronic properties of Ag{sub x}VP{sub 2}O{sub 7} with a wide composition range of 0.7≤x≤1 synthesized newly are explored through measurements of X-ray four-circle diffraction, electrical resistivity, and magnetization. This system is monoclinic with space group P2{sub 1}/c and the lattice constants for x=1 are a=7.3358(3) Å, b=8.0235(3) Å, c=9.5782(5) Å, β=111.940(4)°, and V=522.93(5) Å{sup 3}. The structure is described in terms of VO{sub 6} octahedra which are bridged with P{sub 2}O{sub 7} groups to form a three-dimensional network with the hexagonal tunnels that a pair of Ag ions apparently resides in. The crystal field of V ions is intermediate and the electron configuration has the orbital-singlet ground state with a gap of the order of 10 K to the doublet state. - Graphical abstract: (a) The temperature dependencies of inverse magnetic susceptibilities for Ag{sub x}VP{sub 2}O{sub 7} with x=0.7−1 and (b) the low-temperature susceptibilities. - Highlights: • Ag{sub x}VP{sub 2}O{sub 7} system with 0.7<1 is prepared. • The crystal structure and electronic properties are clarified. • The electron configuration has the orbital-singlet ground state. • The electron hopping and the V–O covalency are reduced significantly. • The Ag deficiency gives rise to the charge separation of V{sup 3+} and V{sup 5+}.
- OSTI ID:
- 22451120
- Journal Information:
- Journal of Solid State Chemistry, Vol. 220; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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