ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The problem of bond length alternation in cyclic polyene models as described by the Pariser-Parr-Pople π-electron Hamiltonian, together with an empirical quasi harmonic σ-core potential is investigated using the unrestricted Hartree-Fock wave function employing different spatial orbitals for different spins. It is shown that in contrast to the restricted Hartree-Fock method, which favors bond alternation in large cyclic polyenes, the unrestricted Hartree-Fock method stabilizes the symmetric structures with equidistant internuclear separation. An assessment of the amount of correlation error recovered by the unrestricted Hartree-Fock procedure is examined and the qualitatively different behavior of the cyclic polyene models when described by restricted and unrestricted Hartree-Fock wave functions is discussed from this viewpoint.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560240406
