Wavefunction-based quantum-chemicalab initiocalculations for core electron binding energies of small open shell...

Core electron binding energies (CEBEs), i.e. ionization energies of 1s core orbitals, are calculated by means of wavefunction-based quantum-chemicalab initiomethods for a series of small open-shell molecules containing first-row atoms. The calculations are performed in three steps: (a) Koopmans' theorem, where the orbitals of the electronic ground state are used unchanged also for the ions, (b) Hartree-Fock or self consistent field (SCF) approximation in which the orbitals are allowed to relax after 1s ionization (ΔSCF), (c) dynamic correlation effects on top of SCF. For open-shell molecules 1s ionization leads to ions in several spin states, mostly to a pair of a triplet and a singlet state. In several cases one or both of these ionic states are only poorly described by a single-reference SCF wavefunction, therefore a multi-reference complete active space self consistent field (CAS-SCF) wavefunction is used instead. The correlation effects are evaluated by means of our multi-reference coupled electron pair approximation program. The accuracy of the calculated CEBEs is in the order of 0.1-0.4 eV. This is in agreement with experimental results for NO and O₂. But there exist only very few gas phase data for CEBEs of open-shell molecules.