Electronic Structures of ANb2PS10 (A=Ag, Na) and AuNb4P2S20

New quaternary compounds $ANb_2PS_{10}$ (A = Na, Ag) and $AuNb_4P_2S_{20}$ were synthesized and characterized. The structures of three compounds consist of one-dimensional infinite chains built by [$Nb_2S_{12}$] and [$PS_4$] units. Cation atoms are occupied within the van der Waals gap of sulfur atoms between infinite chains to make -S…$M^+$…S- contacts. There is only one Au atom site and so crystallographically a unit cell contains four equivalent Au atoms in $AuNb_4P_2S_{20}$. This is only the half of the numbers of Na or Ag atoms in $NaNb_2PS_{10}$ or $AgNb_2PS_{10}$. The ratio between $Nb_2PS_{10}$ matrix vs the cation is, therefore, 1 : 1 for Ag and Na, but it is 2 : 1 for Au. Mixed valency in Au or Nb was expected to balance the charge in the latter compound. The electronic structures calculated based on the extended Huckel tight-binding method show that $ANb_2PS_{10}$ (A = Ag, Na) are semiconducting, while $AuNb_4P_2S_{20}$ is metallic, which is not consistent with the experimental results of these three compounds that all exhibit semiconducting property. The result of calculation suggests that $AuNb_4P_2S_{20}$ might be a magnetic insulator. Magnetic measurement experiment exactly proved that the compound is a Slater antiferromagnetic material with the Neels' temperature of 45 K. It is recognized, therefore, that electronic structure analysis is very useful to understand the properties of compounds.