Potential energy surface and dissociative cleavage of chlorobenzene radical anion
2001; Elsevier BV; Volume: 348; Issue: 5-6 Linguagem: Inglês
10.1016/s0009-2614(01)01171-x
ISSN1873-4448
AutoresIrina V. Beregovaya, Lyudmila N. Shchegoleva,
Tópico(s)Spectroscopy and Quantum Chemical Studies
ResumoPotential energy surface (PES) of the short-lived PhCl− radical anion has been studied by ROHF/6-31+G∗ and MP2/6-31+G∗//ROHF/6-31+G∗ calculations. The PES peculiarities were found to result from two reasons: (a) the quasi-degeneracy of PhCl−π states; (b) the presence of a low-lying repulsive σ term. The anion meta-stable 2Π state has been located, and transition state for C–Cl cleavage has been found revealing an asymmetrical non-planar structure. Possible mechanisms of halobenzene anions dissociative cleavage are discussed, with the PhCl− as a model.
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