Abstract
The photoionization cross section can be expressed as a particular matrix element of the resolvent of the molecular electronic Hamiltonian. By using a mixture of real and complex Gaussian basis functions to form a matrix representation of the Hamiltonian it is possible to use this expression to compute molecular photoionization cross sections from the results of a matrix diagonalization. This procedure is based on a variational principle for the resolvent matrix element from which the photoionization cross section is calculated, and can be applied in the presence of coupling between ionization channels. The interference between resonance features and the electron-ion scattering background is naturally incorporated by this method, and it is easily implemented for polyatomic systems. Results are reported for valence- and K-shell ionization of N2 at the static exchange level which demonstrate the utility of this method for molecular problems. Agreement with most other calculations is adequate and is especially good with those which compute the photoionization cross section directly from the electron-ion scattering wave function. The complex-basis-function technique is particularly successful in reproducing resonance features in these cross sections. A discussion of the variational behavior of the amplitude is given, and it is shown that the variational nature of these calculations provides a useful computational diagonostic. © 1985 The American Physical Society.