Electron–Propagator Calculations with Generalized Hartree–Fock Spin–Orbitals
F. Pawłowski and J. V. Ortiz
Department of Chemistry and Biochemistry Auburn University
Auburn, Alabama 36849-5312
Electron–propagator self–energy approximations in general use for the calculation of electron–binding energies of molecules and molecular ions, such as diagonal second–order (D2), diagonal third–order and renormalized partial–third order (P3+), may be extended to generalized Hartree–Fock reference determinants for the following purposes:
- single–reference calculations with complex spin–orbitals that require multi–reference ground states when restricted spin–orbitals are employed, e.g. ionization energies of 1∆g O2
- two–component calculations with Douglas–Kroll–Hess scalar relativistic terms in the one–electron Hamiltonian and Boettger spin–orbit matrix elements, e.g. electron detachment energies of molecules and anions containing period 4–6 elements of families 15-18 in the periodic table.
Composite models that combine D2 and P3+ results obtained respectively with large and small basis sets show considerable promise for prediction and interpretation of photoelectron spectra.
This work was supported by the National Science Foundation through grant CHE-1565760 to Auburn University.