Intermolecular ground and excited state potential energy surfaces and charge-transfer spectrum of benzene: TCNE electron donor—acceptor complex

The six-dimensional intermolecular potential energy surface of the benzene:tetracyanoethylene (TCNE) electron donor—acceptor (EDA) complex has been explored, using a combination of ab initio and semiempirical quantum mechanical calculations, at 4732 discrete intermolecular geometries. Spectroscopic...

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Bibliographic Details
Published in:Spectrochimica acta. Part A: Molecular spectroscopy 1992-05, Vol.48 (5), p.715-724
Main Authors: Emery, Luke C., Sheldon, Janet M., Edwards, W.Daniel, McHale, Jeanne L.
Format: Article
Language:English
Subjects:
Atomic and molecular physics
Exact sciences and technology
Molecular properties and interactions with photons
Molecular spectra
Physics
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Summary:The six-dimensional intermolecular potential energy surface of the benzene:tetracyanoethylene (TCNE) electron donor—acceptor (EDA) complex has been explored, using a combination of ab initio and semiempirical quantum mechanical calculations, at 4732 discrete intermolecular geometries. Spectroscopic INDO calculations were also performed at a subset of the total sampled configurations. The charge-transfer absorption lineshape was then calculated according to a previously described semiclassical approach, using the improved ab initio potential to average the spectrum over the donor—acceptor distance coordinate, R, in place of the previously employed harmonic approximation. The calculated lineshape was found to be in good agreement with the experimental gas phase optical absorption spectrum.
ISSN:0584-8539
DOI:10.1016/0584-8539(92)80215-I