Abstract
It is demonstrated that the monoexcited configuration interaction matrix, constructed from the localized (or Wannier) orbitals for an one-dimensional extended system with translational symmetry can be used to define a series of finite-dimensional matrices whose lowest eigenvalues and eigenvectors converge to the lowest eigenvalues and eigenvectors of the infinite-dimensional full monoexcited configuration interaction problem. As an illustration, the developed monoexcited configuration interaction approach is applied to the π-electronic model of cyclic polyenes (annulenes) in the framework of the Pariser-Parr-Pople approximation. A standard parametrization scheme has been found to yield a value of ∼2.42 eV for the lowest singlet excitation energy of an infinite polyene, which is in good agreement with the experimental estimate of ∼2 eV.
| Original language | English |
|---|---|
| Pages (from-to) | 8520-8528 |
| Number of pages | 9 |
| Journal | Journal of Chemical Physics |
| Volume | 94 |
| Issue number | 12 |
| Publication status | Published - 1 Jan 1991 |