Contrasting 1D tunnel-structured and 2D layered polymorphs of V sub(2)O sub(5): relating crystal structure and bonding to band gaps and electronic structure

New V sub(2)O sub(5) polymorphs have risen to prominence as a result of their open framework structures, cation intercalation properties, tunable electronic structures, and wide range of applications. The application of these materials and the design of new, useful polymorphs requires understanding their defining structure-property relationships. We present a characterization of the band gap and electronic structure of nanowires of the novel zeta -phase and the orthorhombic alpha -phase of V sub(2)O sub(5) using X-ray spectroscopy and density functional theory calculations. The band gap is found to decrease from 1.90 plus or minus 0.20 eV in the alpha -phase to 1.50 plus or minus 0.20 eV in the zeta -phase, accompanied by the loss of the alpha -phase's characteristic split-off d sub()xyband in the zeta -phase. States of d sub()xyorigin continue to dominate the conduction band edge in the new polymorph but the inequivalence of the vanadium atoms and the increased local symmetry of [VO sub(6)] octahedra results in these states overlapping with the rest of the V 3d conduction band. zeta -V sub(2)O sub(5) exhibits anisotropic conductivity along the b direction, defining a 1D tunnel, in contrast to alpha -V sub(2)O sub(5) where the anisotropic conductivity is along the ablayers. We explain the structural origins of the differences in electronic properties that exist between the alpha - and zeta -phase.