Journal of Chemical Physics, Vol.115, No.10, 4549-4557, 2001
Application of higher order decouplings of the dilated electron propagator to (2)Pi CO-, (2)Pi(g) N-2(-) and (2)Pi(g) C2H2-shape resonances
The full third order (Sigma (3)), quasi-particle third order (Sigma (3)(q)) and outer valence Green's function (OVGF-A) decouplings of the bi-orthogonal dilated electron propagator have been implemented and results from their application to (2)Pi CO-, (2)Pi (g) N-2(-), and (2)Pi (g) C2H2- shape resonances are presented and compared with energies and widths obtained using the zeroth order (Sigma (0)), quasiparticle second order (Sigma (2)(q)) and second order (Sigma (2)) decouplings. The energies and widths from the various Sigma (3) decouplings for shape resonances are close to those obtained using the Sigma (2) approximant but the corresponding Feynman-Dyson amplitudes (FDAs) differ considerably. The differences between FDAs from different decouplings are analyzed to elicit the role of correlation and relaxation in the formation and decay of shape resonances.