We show that the quasi-1D behavior of BaVS 3 can be understood analyzing the X-ray absorption near edge spectra at the sulfur K edge. Linear dichroïsm experiments, analyzed with the help of ab initio calculations, reveal two strong and polarization dependent pre-edge features, induced by the band character of the 3d vanadium levels. They are related to crystal field split t 2g and e g states. When the temperature is lowered, the t 2g feature shifts progressively to higher energy, and its intensity increases for the polarization along the c-axis, stacking direction of the V-S face sharing octahedra. This behavior points to the depletion of sulfur states and thus the lack of S 3p -V 3d hybridization in the direction of V-S chains.
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