title: Key role of bismuth in the magnetoelastic transitions of Ba3BiIr2O9 and Ba3BiRu2O9 as revealed by chemical doping.
abstract: The key role played by bismuth in an average intermediate oxidation state in the magnetoelastic spin-gap compounds Ba3BiRu2O9 and Ba3BiIr2O9 has been confirmed by systematically replacing bismuth with La(3+) and Ce(4+). Through a combination of powder diffraction (neutron and synchrotron), X-ray absorption spectroscopy, and magnetic properties measurements, we show that Ru/Ir cations in Ba3BiRu2O9 and Ba3BiIr2O9 have oxidation states between +4 and +4.5, suggesting that Bi cations exist in an unusual average oxidation state intermediate between the conventional +3 and +5 states (which is confirmed by the Bi L3-edge spectrum of Ba3BiRu2O9). Precise measurements of lattice parameters from synchrotron diffraction are consistent with the presence of intermediate oxidation state bismuth cations throughout the doping ranges. We find that relatively small amounts of doping (∼10 at%) on the bismuth site suppress and then completely eliminate the sharp structural and magnetic transitions observed in pure Ba3BiRu2O9 and Ba3BiIr2O9, strongly suggesting that the unstable electronic state of bismuth plays a critical role in the behavior of these materials.
authors.affiliation: School of Chemistry, The University of Sydney , Sydney, New South Wales 2006, Australia.
authors.forename: Peter E R
authors.initials: PE
authors.lastname: Blanchard
authors.forename: Zixin
authors.initials: Z
authors.lastname: Huang
authors.forename: Brendan J
authors.initials: BJ
authors.lastname: Kennedy
authors.forename: Samuel
authors.initials: S
authors.lastname: Liu
authors.forename: Wojciech
authors.initials: W
authors.lastname: Miiller
authors.forename: Emily
authors.initials: E
authors.lastname: Reynolds
authors.forename: Qingdi
authors.initials: Q
authors.lastname: Zhou
authors.forename: Maxim
authors.initials: M
authors.lastname: Avdeev
authors.forename: Zhaoming
authors.initials: Z
authors.lastname: Zhang
authors.forename: Jade B
authors.initials: JB
authors.lastname: Aitken
authors.forename: Bruce C C
authors.initials: BC
authors.lastname: Cowie
authors.forename: Ling-Yun
authors.initials: LY
authors.lastname: Jang
authors.forename: Thiam Teck
authors.initials: TT
authors.lastname: Tan
authors.forename: Sean
authors.initials: S
authors.lastname: Li
authors.forename: Chris D
authors.initials: CD
authors.lastname: Ling