  Polynitrogen compounds have attracted great interest due to their potential
applications as high energy density materials. Most recently, a rich variety of
alkali polynitrogens (R_{x}N_{y}; R=Li, Na, and Cs) have been predicted to be
stable at high pressures and one of them, CsN_{5} has been recently
synthesized. In this work, various potassium polynitrides are investigated
using first-principles crystal structure search methods. Several novel
molecular crystals consisting of N_{4} chains, N_{5} rings, and N_{6} rings
stable at high pressures are discovered. In addition, an unusual nitrogen-rich
metallic crystal with stoichiometry K_{2}N_{16} consisting of a planar
two-dimensional extended network of nitrogen atoms arranged in fused eighteen
atom rings is found to be stable above 70 GPa. An appreciable electron transfer
from K to N atoms is responsible for the appearance of unexpected chemical
bonding in these crystals. The thermodynamic stability and high pressure phase
diagram is constructed. The electronic and vibrational properties of the
layered polynitrogen K_{2}N_{16} compound are investigated, and the
pressure-dependent IR-spectrum is obtained to assist in experimental discovery
of this new high-nitrogen content material.
