Application of the multiconfiguration time‐dependent Hartree–Fock method to CH + : The auxiliary active space Academic Article uri icon

abstract

  • The multiconfigurational time-dependent Hartree-Fock (MCTDHF) method is used to study the excitation energies and transition moments of the CH + ion. A consistent approach to the selection of configurations based on the complete active space (CAS) model is successfully applied. In this approach a large set of orbitals is included in the active space without a substantial increase in the number of configurations, since only for a smaller subset of orbitals is the configuration expansion complete and the remaining orbitals active are considered an auxiliary set. For CH + the active space includes the valence and additional orbitals, with the valence orbitals constituting the complete subset. Extra configurations involving single and double excitations from the valence to the additional (auxiliary) orbitals are included both for the MCSCF reference state and in the MCTDHF. It is demonstrated that this active space accurately mimics MCSCF and MCTDHF calculations with an enlarged complete active space which includes both the original CAS and the auxiliary orbitals. The calculations for the 1Π and 1Σ + excited states at the equilibrium geometry show that accurate excitation energies and transition moments are obtained in this way. For most of these states for which there are other good ab initio results available, we obtain comparable excitation energies and transition moments. In addition to 1Π and 1Σ +, low lying states of other symmetries are obtained and discussed. © 1988 American Institute of Physics.

author list (cited authors)

  • Jaszuński, M., Rizzo, A., & Yeager, D. L.

citation count

  • 11

publication date

  • September 1988