Lanczos-based equation-of-motion coupled-cluster singles-and-doubles approach to the total photoionization cross section of valence excited states.

Abstract

Excitation energies and oscillator strengths of the first two electronically excited states of helium, water, sulfur dioxide, molecular nitrogen, and carbon monoxide were obtained from an asymmetric-Lanczos-based formulation of the equation-of-motion coupled cluster singles and doubles approach. The total photoionization cross sections were generated by two different methodologies: an analytic continuation procedure based on the Padé approximants and the Stieltjes imaging technique. The results are compared with theoretical photoionization cross sections from algebraic diagrammatic construction [ADC(2)] and ADC(2)-x calculations [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] and with available experimental data.