Photoelectron matrix elements which yield the probability to find a system in a specific final state for a given initial state are used for calculating many spectroscopically important quantities, including PADs, total and differential ionization cross-sections. Under strong orthogonality conditions, one can express photoelectron matrix elements using Dyson orbitals, the objects representing an overlap between initial N-electron and final (N-1)-electron wavefunctions for the ionization process [1]. Dyson orbitals can be computed for any initial and final many-electron  wavefunctions, however, EOM-CC formalism provides a straightforward way of their evaluation as well as including correlation and orbital relaxation effects. In combination with describing the wavefunction of outgoing electron as linear combination of spherical waves, this allows to compute energy dependence of ionization cross-sections. The method is used for explaining the trends in the experimental photoelectron spectra of aqueous phenol and phenolate [2].1. C.M. Oana, A.I. Krylov. J. Chem. Phys. 127, 234106 (2007)2. D.Ghosh, A.Roy, R.Seidel, B.Winter, S.Bradforth, A.I.Krylov. J. Phys. Chem. B 116, 7269 (2012)

Dyson orbitals for calculating photoionization cross-sections

248th National Meeting (2014)

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