Theoretical Study on the Structures and Electronic Spectra of TCNE2

• Published in: Chemphyschem Vol. 7; no. 2; pp. 508 - 513
• Main Authors: Cuesta, Inmaculada García, Sánchez‐Marín, José, Sánchez de Merás, Alfredo M. J.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag 13.02.2006; Wiley
• Subjects: Ab initio calculations; anions; Atomic and molecular physics; Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations); charge transfer; electronic structure; Electronic structure of atoms, molecules and their ions: theory; Exact sciences and technology; Physics; solvent effects; Chemical solution; Organic anion; Electronic structure; Tetracyanoethylene; Theoretical study; Organic dianion; Electronic transition; Ab initio calculations; Charge transfer transition; anions; charge transfer; Solvent effects
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.200500468

10.1002/cphc.200500468.absInvestigations into the charge‐separated states and electron‐transfer transitions in tetracyanoethylene (TCNE) complexes have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE2−has D2dsymmetry in vacuum as well as in the solvents dichloromethane and acetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoretical results are compared to the experimental data and good agreement is achieved. Stable geometric structures: The experimental electronic spectrum of the tetracyanoethylene dianion (TCNE2−; see figure) exhibits different features in dichloromethane and acetonitrile due to solute–solvent interactions. The authors use coupled cluster (CC) calculations which include the effects of the solvent to theoretically generate the spectra and elucidate the different geometrical structures adopted.