Benchmark Full Configuration Interaction Calculations on the Lowest-Energy (2)P and (4)P States of the Three-Electron Harmonium Atom.

Abstract

Full configuration interaction calculations carried out in conjunction with careful optimization of basis sets and judicious extrapolation schemes for 12 values of the confinement strength ω ranging from 0.1 to 1000.0 provide benchmark energies for the (2)P ground state and the (4)P first excited state of the three-electron harmonium atom, allowing for numerical verification of the recently obtained second-order energy coefficients and confirming the few available results of Monte Carlo studies. The final energy values, obtained by correcting the extrapolated data for residual errors in the low-order energy coefficients, possess accuracy of ca. 20 μHartree for the doublet state and ca. 10 μHartree for the quartet one, making them suitable for calibration and testing of approximate electron correlation methods of quantum chemistry. The energy limits for individual angular momenta ranging from 1 to 4 are also available, facilitating comparisons with results of calculations involving finite basis sets. An example of application involving the BLYP and B3LYP functionals is provided.