Theoretical Prediction of Benzyne-Like Species in Pyrene Diradicals

Autor:	Francesc Illas, J. M. Bofill, J. M. Martínez‐Magadán, Isidoro García-Cruz
Rok vydání:	2004
Předmět:	chemistry.chemical_compound Chemistry Diradical Computational chemistry Pyrene Density functional theory Electronic structure Singlet state Physics::Chemical Physics Physical and Theoretical Chemistry Wave function Ground state Aryne
Zdroj:	The Journal of Physical Chemistry A. 108:5111-5116
ISSN:	1520-5215 1089-5639
DOI:	10.1021/jp037795r
Popis:	The different products that can be obtained from pyrene dehydrogenation have been studied by means of hybrid density functional theory. Most of the didehydrogenated species exhibit a diradical character. This is supported by the closeness between the geometry and energy of singlet and triplet states and the open-shell nature of the singlet state. However, three didehydrogenated species have been found to exhibit a closed-shell singlet electronic ground state. The analysis of the electronic structure, the formation energy of these didehydrogenated species, and their geometrical structure reveals that these three didehydrogenated species are better described as benzyne-like moieties; two of them are of o- and one of m-benzyne character. The two o-benzyne species have lower energies than the m-benzyne and are favored upon diradical formation. This interpretation is fully supported by the analysis of multiconfigurational wave functions and the order of stabilities confirmed by second-order multireference pert...
Databáze:	OpenAIRE
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