Electronic structure ofLi3N

We present the results of a self-consistent calculation of the electronic structure of the fast ionic conductor lithium nitride (${\mathrm{Li}}_3$N). The first-principles pseudopotential method is used to obtain the band structure, the charge density, and the density of states at zero temperature. Apart from treating the nitrogen and the lithium $1s$ state in the frozen core approximation, no ad hoc assumptions on the electron density are made. The calculation confirms the ionic picture of the chemical bonding in ${\mathrm{Li}}_3$N. A negative charge of approximately 2.8 electrons can be associated with each nitrogen atom. The calculated ground-state wave functions are used to obtain the autocorrelation function of the one-electron density matrix. The observed anisotropies in the autocorrelation function are quantitatively reproduced.