The generalized valence bond π orbitals of ethylene and allyl cation

Abstract

Using a fixed sigma core obtained from full electron ab initio Hartree-Fock calculations, the spatially projected GVB orbitals for the pi electron systems of ethylene and allyl cation are reported. The GVB(SP) method generates wavefunctions possessing the correct spatial and spin symmetry without restricting the nature of the individual orbitals. The GVB(SP) wavefunction provides a simple interpretation of the molecule in terms of orbitals each containing a single electron. The resulting total energies and excitation energies agree very well with full configuration interaction calculations.