Electron Momentum Spectroscopy of pyrimidine at the benchmark ADC(3) level

Abstract

An extensive study of the valence electronic structure, ionization spectrum and electron momentum distributions of pyrimidine is presented, on the ground of accurate calculations of one-electron and shake-up ionization energies and of the related Dyson orbitals, using one-particle Green's Function theory in conjunction with the third-order Algebraic Diagrammatic Construction scheme [ADC( 3)]. Comparison is made with results obtained from standard (B3LYP) Kohn-Sham orbitals and recent measurements employing Electron Momentum Spectroscopy. Quantitative insights into the experimental momentum distributions are amenable without resorting to any empirical rescaling of pole strengths, provided band overlaps and relaxation effects are properly accounted for. (C) 2010 Elsevier B.V. All rights reserved.