  Drawing the analogy to BaBiO3, we investigate via ab-initio electronic
structure calculations potential new superconductors of the type ATlX3 with A =
Rb, Cs and X = F, Cl, and Br, with a particular emphasis on RbTlCl3. Based on
chemical reasoning, supported by the calculations, we show that Tl-based
perovskites have structural and charge instabilities driven by the lone pair
effect, similar to the case of BaBiO3, effectively becoming A2Tl1+Tl3+X6. We
find that upon hole doping of RbTlCl3, structures without Tl1+, Tl3+ charge
disproportionation become more stable, although the ideal cubic perovskite,
often viewed as the best host for superconductivity, should not be the most
stable phase in the system. The known superconductor (Sr,K)BiO3 and hole doped
RbTlCl3, predicted to be most stable in the same tetragonal structure, display
highly analogous calculated electronic band structures.
