The electronic structure of molecules by a many-body approach: V. Ionization potentials and one-electron properties of cyclopentadiene and 1-sila-cyclopentadiene-(2,4)

Abstract

The valence ionization potentials (IP's) of cyclopentadiene and 1-sila-cyclopentadiene-(2,4) are studied by an ab initio many-body approach which includes the effect of electron correlation and reorganization beyond the Hartree-Fock approximation. The Hartree-Fock approximation gives the correct ordering of the IP's for cyclopentadiene but this ordering does not agree with the results of the previous experimental and theoretical studies. The ordering is 1a 2(π), 2b 1(π), 4b 2, 6a 1, 5a 1, 3b 2, 1b 1 (π), 4a 1, 2b 2, 3a 1. For sila-cyclopentadiene the ordering of the IP's is: 1a 2(π), 4b 2, 2b 1(π), 6a 1, 1b 1(π), 5a 1, 3b 2, 4a 1, 3a 1, 2b 2. The Hartree-Fock approximation is found to be incorrect with respect to the ordering of the 4b 2 and 2b 1(π) IP's. A number of one-electron properties are calculated in the one-particle approximation and compared with the available experimental data.