Hg₂NF, Analogue of HgO

Substitution of aliovalent anions in metal oxides imparts significant changes to the electronic structure of the materials. We have been able to fully substitute N 3– and F – in place of O 2– to obtain Hg 2 NF. Hg 2 NF is isostructural with orthorhombic HgO (mineral montroydite). The bond lengths of Hg 2 NF obtained by Rietveld refinement are dissimilar and the optical band gap of Hg 2 NF (2.56 eV) is higher than that of HgO (2.2 eV). The elemental composition of Hg, N, and F were obtained by X‐ray photoelectron spectroscopy and found to be 2:1:1. First‐principles calculations show Hg 2 NF to be a direct band gap semiconductor with the valence band consisting mainly of N (2p) orbitals. The conduction band minimum (CBM) has a mixed contribution from Hg‐6 s and N‐2 p orbitals. The lowest energy band has a dominant contribution from Hg‐5 d states in all the configurations.