Collect. Czech. Chem. Commun. 1979, 44, 3041-3071

Third-order energy using CNDO/2 and INDO Hamiltonian approximations in the modified PCILO method

Roman Boča

Department of Inorganic Chemistry, Slovak Institute of Technology, 880 37 Bratislava


The perturbative configuration interaction using strictly localized molecular orbitals, called the modified PCILO method has been applied in this communication for the calculations of the energy terms of 15 small molecules up to the third order of the perturbation theory. For this method the use of the Rayleigh-Schrodinger many-body perturbation theory with the Moller-Plesset type of the Hamiltonian partitioning is characteristic. On the CNDO/2 and INDO level of approximations the strictly localized molecular orbitals have been constructed by solving the modified 2 x 2 Roothaan's equations. From the zeroth order ground-state wave function the charge distributions, dipole moments and carbon 13-proton nuclear spin-spin coupling constants have been calculated. Results show that the chemical formula, represented with the zeroth order of the perturbation theory, is a good order of the approximation for the study of the molecule. For diatomic molecules the equilibrium interatomic distances and harmonic force constants have been calculated up to the third order of the perturbation theory. The second order of the perturbation theory provides results which are very near to the MO-LCAO-SCF calculations. The main advantage of the PCILO method lies in much saving of the computing time.