Accurate Atomic Correlation and Total Energies for Correlation-Consistent Effective Core Potentials II: Rb-Xe Elements.

We employ correlation-consistent effective core potentials (ccECPs) to perform exact or nearly exact correlation and total energy calculations for the fifth-row elements (Rb-Xe). Total energies are calculated using various correlated methods: configuration interaction (CI), coupled-cluster (CC) up to perturbative quadruple excitations whenever feasible, and stochastic quantum Monte Carlo (QMC) approaches. In order to estimate the energy at the complete basis set (CBS) limit, the basis sets are employed systematically through aug-cc-p(C)VnZ for each ccECP and further extrapolated to the CBS limit within the corresponding methods. Kinetic energies are evaluated at the FCI/CISD level to provide insights into the electron density and localization of the ccECPs. We also provide data sets for the widely used diffusion Monte Carlo (DMC) to quantify fixed-node biases with single-reference trial wave functions. These comprehensive benchmarks validate the accuracy of ccECPs within the CC, CI, and QMC methodologies, thereby providing accurate and tested valence-only Hamiltonians for many-body electronic structure calculations.