The merger of density-functional theory in the local density approximation and many-body dynamical mean-field theory allows for an ab initio calculation of Ce including the inherent $4f$ electronic correlations. We solve the equations by the quantum Monte Carlo technique and calculate the Ce energy, spectrum, and double occupancy as a function of volume. At low temperatures, the correlation energy exhibits an anomalous region of negative curvature which drives the system towards a thermodynamic instability, i.e., the $\gamma$-to- $\alpha$ volume collapse, consistent with experiment. The connection of the energetic with the spectral evolution shows that the physical origin of the energy anomaly and, thus, the volume collapse is the appearance of a quasiparticle resonance in the $4f$-spectrum which is accompanied by a rapid growth in the double occupancy.

• Received 28 June 2001

DOI:https://doi.org/10.1103/PhysRevLett.87.276404