Ionization Energies and Dyson Orbitals of the Iso-electronic SO2, O3, and S3 Molecules from Electron Propagator Calculations.

Abstract

Adiabatic and vertical ionization energies corresponding to the X̃ , à , and B̃ final states of SO2+, O3+, and S3+ have been calculated with a variety of electron-propagator and coupled-cluster methods. The BD-T1 electron-propagator method for vertical ionization energies and coupled-cluster adiabatic and zero-point corrections yield agreement with experiment to within 0.1 eV in all cases but one. The remaining discrepancies for the à state of SO2+ indicate a need for higher levels of theory in determining cationic minima and their accompanying vibrational frequencies. Predictions for the still unobserved à and B̃ final states of S3+ are included. To account for increased biradical character in O3 and S3, highly correlated reference states are required to produce the correct order of final states. Electron correlation plays a subtle role in determining the contours of the Dyson orbitals obtained with BD-T1 and NR2 electron-propagator calculations.