Intermolecular and intramolecular interactions calculated with ab initio perturbative configuration interaction method using strongly localized orbitals

✍ Scribed by P. Otto; J. Ladik

• Publisher: John Wiley and Sons
• Year: 1982
• Tongue: English
• Weight: 776 KB
• Volume: 22
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.560220115

✦ Synopsis

Abstract

We have applied the ab initio formulation of the perturbative configuration interaction using localized orbitals (PCILO) method up to third order to calculate intermolecular and intramolecular interaction energies going beyond the ab initio Hartree–Fock calculation. For the rotational barrier in ethane our results agree well with the experimental value and the cis‐ and even the trans‐barriers in HOOH are at least qualitatively reproduced with the aid of the STO‐3__G__ basis set. In the case of the water dimer we obtain an equilibrium intermolecular distance and interaction energy which are confirmed by other calculations. We can further conclude from our studies that one has to include higher orders in the perturbation expansion as the system becomes more complicated. It is especially the last aspect which hinders the application of the ab initio PCILO to estimate the major part of the electron correlation energy for large molecules.