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Bazante AP, Davidson ER, Bartlett RJ. The benzene radical anion: A computationally demanding prototype for aromatic anions. J Chem Phys. 2015;142(20):204304doi: 10.1063/1.4921261.
Bazante, A. P., Davidson, E. R., & Bartlett, R. J. (2015). The benzene radical anion: A computationally demanding prototype for aromatic anions. The Journal of chemical physics, 142(20), 204304. https://doi.org/10.1063/1.4921261
Bazante, Alexandre P, et al. "The benzene radical anion: A computationally demanding prototype for aromatic anions." The Journal of chemical physics vol. 142,20 (2015): 204304. doi: https://doi.org/10.1063/1.4921261
Bazante AP, Davidson ER, Bartlett RJ. The benzene radical anion: A computationally demanding prototype for aromatic anions. J Chem Phys. 2015 May 28;142(20):204304. doi: 10.1063/1.4921261. PMID: 26026444.
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J Chem Phys. 2015 May 28;142(20):204304. doi: 10.1063/1.4921261.

The benzene radical anion: A computationally demanding prototype for aromatic anions.

The Journal of chemical physics

Alexandre P Bazante, E R Davidson, Rodney J Bartlett

Affiliations

  1. Quantum Theory Project, University of Florida, Gainesville, Florida 32611, USA.
  2. Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.

PMID: 26026444 DOI: 10.1063/1.4921261

Abstract

The benzene radical anion is studied with ab initio coupled-cluster theory in large basis sets. Unlike the usual assumption, we find that, at the level of theory investigated, the minimum energy geometry is non-planar with tetrahedral distortion at two opposite carbon atoms. The anion is well known for its instability to auto-ionization which poses computational challenges to determine its properties. Despite the importance of the benzene radical anion, the considerable attention it has received in the literature so far has failed to address the details of its structure and shape-resonance character at a high level of theory. Here, we examine the dynamic Jahn-Teller effect and its impact on the anion potential energy surface. We find that a minimum energy geometry of C2 symmetry is located below one D2h stationary point on a C2h pseudo-rotation surface. The applicability of standard wave function methods to an unbound anion is assessed with the stabilization method. The isotropic hyperfine splitting constants (Aiso) are computed and compared to data obtained from experimental electron spin resonance experiments. Satisfactory agreement with experiment is obtained with coupled-cluster theory and large basis sets such as cc-pCVQZ.

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