Calculating molecular Rydberg states using the one-particle Green's function: application to HCO and C(NH2)3.
A simple but accurate and computationally efficient method for routine ab initio calculations of molecular Rydberg states is described. The method, which can be applied to Rydberg states associated with a nondegenerate ion core, consists in the self-consistent solution of an effective one-electron problem. First, the restricted Hartree-Fock problem of the ion core is solved. The orbital energies and certain two-electron Coulomb matrix elements with respect to the molecular orbital basis are then used to construct an energy-dependent many-body correction to the Hartree-Fock mean field. This correction is derived from the Dyson equation satisfied by the one-particle Green's function. The method is applied to calculate Rydberg potential-energy curves of HCO. The presented data confirm and extend recent large-scale multireference configuration-interaction calculations and help develop a detailed theoretical description of the astrophysically important dissociative recombination of a low-energy electron with HCO(+). As further illustration of the utility of the method, the first ab initio calculations of the excited states of an electron bound to the guanidinium cation [C(NH(2))(3)](+) are reported.
Feuerbacher
Sven
S
Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
Santra
Robin
R