Perturbative configuration interaction using localized orbitals in the INDO hypothesis. I. Theory and applications to energetical problems

A complete development of the PCILO method is presented for the INDO approximation. The introduction of exchange terms in the theoretical treatment is discussed and a detailed analysis of the successive contributions to the total energy is given. The method is applied to various conformational problems (geometry optimization, rotation, and inversion barriers). Its ability to deal with biological systems is tested on the acetylcholine neurotransmitter. Inversion barriers are highly improved with respect to the corresponding CNDO algorithm. A better account of σ‐π exchange phenomena can be expected with the presented PCILO‐INDO development.