Rydberg states with quantum Monte Carlo

Calculations on Rydberg states are performed using quantum Monte Carlo methods. Excitation energies and singlet-triplet splittings are calculated for two model systems, the carbon atom (P-3 and P-1) and carbon monoxide ((1)Sigma and (3)Sigma). Kohn-Sham wave functions constructed from open-shell localized Hartree-Fock orbitals are used as trial and guide functions. The fixed-node diffusion quantum Monte Carlo (FN-DMC) method depends strongly on the wave function's nodal hypersurface. Nodal artefacts are investigated for the ground state of the carbon atom. Their effect on the FN-DMC results can be analyzed quantitatively. FN-DMC leads to accurate excitation energies but to less accurate singlet-triplet splittings. Variational Monte Carlo calculations are able to reproduce the experimental results for both the excitation energies and the singlet-triplet splittings. (c) 2006 American Institute of Physics.