Electronic symmetry breaking in polyatomic molecules. Multiconfiguration self-consistent field study of the cyclopropenyl radical C3H3

• Published in: The Journal of chemical physics 1984, Vol.80 (1), p.338-343
• Main Authors: HOFFMANN, M. R, LAIDIG, W. D, KIM, K. S, FOX, D. J, SCHAEFER, H. F. III
• Format: Article
• Language: English
• Subjects: Atomic and molecular physics; Electron correlation calculations for atoms and molecules; Electronic structure of atoms, molecules and their ions: theory; Exact sciences and technology; Physics
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.446452

For equilateral triangle geometries (point group D3h), the C3H3 radical has a degenerate 2E″ electronic ground state. Although the 2A2 and 2B1 components separate in energy for C2v geometries, these two components should have identical energies for equilateral triangle structures. In fact, when approximate wave functions are used and the orbitals not required to transform according to the D3h irreducible representations, an energy separation between the 2A2 and 2B1 components is observed. At the single configuration self-consistent field (SCF) level of theory this separation is 2.8 kcal with a double-zeta basis set and 2.4 kcal with double-zeta plus polarization. It has been demonstrated that this spurious separation may be greatly reduced using multiconfiguration self-consistent field (up to 7474 variationally optimum configurations) and configuration interaction (up to 60 685 space and spin adapted configurations) techniques. Configurations differing by three and four electrons from the Hartree–Fock reference function are found necessary to reduce the 2A2-2B1 separation to below 0.5 kcal.