An Auxiliary-Field Quantum Monte Carlo Study of the Chromium Dimer

Abstract

The chromium dimer (Cr2) presents an outstanding challenge for many-body electronic structure methods. Its complicated nature of binding, with a formal sextuple bond and an unusual potential energy curve, is emblematic of the competing tendencies and delicate balance found in many strongly correlated materials. We present a near-exact calculation of the potential energy curve (PEC) and ground state properties of Cr2, using the auxiliary-field quantum Monte Carlo (AFQMC) method. Unconstrained, exact AFQMC calculations are first carried out for a medium-sized but realistic basis set. Elimination of the remaining finite-basis errors and extrapolation to the complete basis set (CBS) limit is then achieved with a combination of phaseless and exact AFQMC calculations. Final results for the PEC and spectroscopic constants are in excellent agreement with experiment.