Density functional study of 1,3,5-trinitro-1,3,5-triazine molecular crystal with van der Waals interactions

Volume dependence of the total energy and vibrational properties of crystalline l,3,5-trinitro-l,3,5-triazine (RDX) are calculated using the density functional theory (DFT). For this molecular crystal, properties calculated with a generalized gradient approximation to the exchange-correlation energy differ drastically from experimental values. This discrepancy arises from the inadequacy in treating weak van der Waals (vdW) interactions between molecules in the crystal, and an empirical vdW correction to DFT (DFT-D approach by Grimme) is shown to account for the dispersion effects accurately for the RDX crystal, while incurring little computational overhead. The nonempirical van der Waals density-functional (vdW-DF) method also provides an accurate description of the vdW corrections but with orders-of-magnitude more computation. We find that the vibrational properties of RDX are affected in a nontrivial manner by the vdW correction due to its dual role-reduction of the equilibrium volume and additional atomic forces.