Cohesive properties of CeN and LaN from first principles

Abstract

The effect of electron-correlation on the ground-state properties of CeN and LaN is studied by ab initio quantum-chemical methods. The approach which is used combines two separate steps: (1) the ground-state Hartree-Fock calculations for the crystal; (2) application of the method of increments to the studied system, which allows an expansion of bulk properties using the information from quantum-chemical calculations performed for finite clusters. As can be expected, for CeN correlation plays a significant role: with Hartree-Fock method only 49% of the experimental cohesive energy has been recovered, whereas after correlation corrections (coupled-cluster approach) the ground-state properties were found to be in good agreement with the experimental data found in literature. Thus, we obtained about 90% of the expected cohesive energy; the computed lattice constants and bulk moduli also agree well with the experimental values. For comparison, the equivalent treatment has been performed for LaN, where no f orbital is occupied. There the HF contribution to the ground-state properties is larger and hence the correlation effects weaker.