Pressure-induced intermetallic valence transition in BiNiO3.
The valence state change of BiNiO3 perovskite under pressure has been investigated by a powder neutron diffraction study and electronic-state calculations. At ambient pressure, BiNiO3 has the unusual charge distribution Bi(3+)(0.5)Bi(5+)(0.5)Ni(2+)O3 with ordering of Bi(3+) and Bi(5+)charges on the A sites of a highly distorted perovskite structure. High-pressure neutron diffraction measurements and bond valence sum calculations show that the pressure-induced melting of the charge disproportionated state leads to a simultaneous charge transfer from Ni to Bi, so that the high-pressure phase is metallic Bi(3+)Ni(3+)O3. This unprecedented charge transfer between A and B site cations coupled to electronic instabilities at both sites leads to a variety of ground states, and it is predicted that a Ni-charge disproportionated state should also be observable.
Azuma
Masaki
M
Institute for Chemical Research, Kyoto University, Uji, Kyoto-fu 611-0011, Japan. masaki@scl.kyoto-u.ac.jp
Carlsson
Sandra
S
Rodgers
Jennifer
J
Tucker
Matthew G
MG
Tsujimoto
Masahiko
M
Ishiwata
Shintaro
S
Isoda
Seiji
S
Shimakawa
Yuichi
Y
Takano
Mikio
M
Attfield
J Paul
JP