Takat B. Rawal

The symmetry-resolved electronic structure of 2H-WSe2(0 0 0 1)

The orbital symmetry of the band structure of 2H-WSe2(0 0 0 1) has been investigated by means of angle-resolved photoelectron spectroscopy (ARPES) and density functional theory (DFT). The WSe2(0 0 0 1) experimental band structure is found, by ARPES, to be significantly different for states of even and odd reflection parities along both the [Formula: see text]-[Formula: see text] and [Formula: see text]-[Formula: see text] lines, in good agreement with results obtained from DFT. The light polarization dependence of the photoemission intensities from the top of the valence band for bulk WSe2(0 0 0 1) is explained by the dominance of W 5[Formula: see text] states around the [Formula: see text]-point and W 5d xy states around the [Formula: see text]-point, thus dominated, respectively, by states of even and odd symmetry, with respect to the [Formula: see text]-[Formula: see text] line. The splitting of the topmost valence band at [Formula: see text], due to spin-orbit coupling, is measured to be 0.49  ±  0.01 eV, in agreement with the 0.48 eV value from DFT, and prior measurements for the bulk single crystal WSe2(0 0 0 1), albeit slightly smaller than the 0.513  ±  0.01 eV observed for monolayer WSe2.

MoS2-supported gold nanoparticle for CO hydrogenation

Employing dispersion-corrected density functional theory, we examine the geometry, electronic structure, and reactivity of 13-atom Au nanoparticle supported on defect-laden single-layer MoS2. The planar structure of Au13 favored in isolated phase, transforms into the three-dimensional structure when supported on MoS2. We find that charge is transferred from MoS2 to Au13, and that the electron density is also distributed away from the Au13/MoS2 interfacial region-making Au sites away from the interface catalytically active. Owing to effect of the support, the Au d states become narrower, and the frontier states appear close to the Fermi level. Consequently, in contrast to the reactivity of Au13/TiO2 toward methanol decomposition, Au13/MoS2 offers excellent activity toward methanol synthesis, as demonstrated here, via CO hydrogenation.