Interchannel coupling and ground state correlation effects in the photoionization of CO

Abstract

We describe a general procedure for applying the complex Kohn variational method to the calculation of molecular photoionization cross sections and asymmetry parameters. In this initial application of the method, we examine the effects of interchannel coupling and ground state correlation on the X 2Σ+(5σ−1), A 2Π(1π−1), and B 2Σ+(4σ−1) partial photoionization cross sections and asymmetry parameters for the CO molecule. We find that the dominant effect of interchannel coupling is to remove a spurious π→π* resonance feature from the continuum that appears at the frozen-core Hartree–Fock level. We also find that it appears to be important to combine the effects of final channel coupling with a correlated initial target state to achieve quantitatively correct cross sections.