A note on the importance of d orbitals in the calculation of effective interactions and the excitation spectra of atoms and molecules

Abstract

AbstractThe focal point of our discussion is the examination of truncated basis sets used in obtaining an accurate first principles clculation of the effective valence shell Hamiltonian by the canonical transformation‐cluster expansion approasch. Subsequent diagonalization of this effecitve valence shell hamiltonian yields the valence shell transition energies. A detailed analysis of numerical results obtained using a number of different basis sets of hydrogen‐like orbitals together with rigorous symmetry arguments celarly demonstrates the special role played by d orbitals in computing the 3P → 1D transition energy in carbon. The failure of early attempts to calculate the effective Hamiltonian for ethylene from first principles is examined in the light of recent ab initio calculations on ethylene involving d orbitals and the computations reported in this paper. We conclude that accurate calculations of the effective valence shell Hamiltonian for molecules must consider d orbitals in the excited orbital basis set.