Study of the Electronic Structure of Molecules. III. Pyrrole Ground-State Wavefunction

作者：Enrico Clementi, H. Clementi, Daly Davis · 发表于：The Journal of Chemical Physics · 年份：1967 · DOI：10.1063/1.1840626 · 被引用次数：146 · 研究领域：Photochemistry and Electron Transfer Studies、Spectroscopy and Quantum Chemical Studies、Spectroscopy and Laser Applications

An SCF LCAO MO ground-state wavefunction is presented for the pyrrole molecule. All electrons, σ and π, are considered, and all the necessary many-center integrals are included in this work. The analysis of the wavefunction reveals that there is a strong two-way charge transfer on the nitrogen atom. (This reopens the problem of the validity of π-electron computations, as discussed in the paper.) The lowest π-electron MO is below the highest σ electron. The hybridization of the σ electrons in the carbon and nitrogen atoms is not s1p2, but deviates strongly for the nitrogen atom and slightly for the carbon atoms.