2015
DOI: 10.1063/1.4921261
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The benzene radical anion: A computationally demanding prototype for aromatic anions

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 literat… Show more

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Cited by 30 publications
(39 citation statements)
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“…Our values for the position and width of the 2 E 2u resonance of the benzene anion (E R = 1.64 eV, Γ = 0.04 eV) also show reasonable agreement with experimental results 91 (E R = 1.12 eV, Γ ≈ 0.12 eV) and EOM-EA-CCSD values obtained with the stabilization method. 85,92 However, for the higher-lying 2 B 2g resonance of the benzene anion, we observe a substantial discrepancy between our results (E R = 6.75 eV, Γ = 0.35 eV), EOM-EA-CCSD stabilization calculations 92 (E R = 5.93 eV), and experiment 91 (E R = 4.82 eV). A possible reason could be that the 2 B 2g resonance is not fully stabilized in our calculations and is affected by the artificial stabilization of a lower-lying pseudocontinuum state.…”
Section: Fig 3 Cap-eom-ea-ccsd Dyson Orbitals Of Various Transient contrasting
confidence: 94%
“…Our values for the position and width of the 2 E 2u resonance of the benzene anion (E R = 1.64 eV, Γ = 0.04 eV) also show reasonable agreement with experimental results 91 (E R = 1.12 eV, Γ ≈ 0.12 eV) and EOM-EA-CCSD values obtained with the stabilization method. 85,92 However, for the higher-lying 2 B 2g resonance of the benzene anion, we observe a substantial discrepancy between our results (E R = 6.75 eV, Γ = 0.35 eV), EOM-EA-CCSD stabilization calculations 92 (E R = 5.93 eV), and experiment 91 (E R = 4.82 eV). A possible reason could be that the 2 B 2g resonance is not fully stabilized in our calculations and is affected by the artificial stabilization of a lower-lying pseudocontinuum state.…”
Section: Fig 3 Cap-eom-ea-ccsd Dyson Orbitals Of Various Transient contrasting
confidence: 94%
“…50 Another orbital stabilization study using DFT gave similar positions. 61 Our results for the position of the shape 2 B 2g resonance at the EOM-EA-CCSD and MR-CISD levels are in good agreement with the previous study at the EOM-EA-CCSD level, 50 even though we used smaller basis sets. They are however still 1 eV off when compared to the experiment,…”
Section: Multi-reference Resultsmentioning
confidence: 77%
“…64,67 Orbital stabilization method using EOM-EA-CCSD on the other hand gave a value of 5.9 eV and a width of 1.4 eV. 50 Another orbital stabilization study using DFT gave similar positions. 61 Our results for the position of the shape 2 B 2g resonance at the EOM-EA-CCSD and MR-CISD levels are in good agreement with the previous study at the EOM-EA-CCSD level, 50 even though we used smaller basis sets.…”
Section: Multi-reference Resultsmentioning
confidence: 95%
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“…39) or even C 2 (Ref. 40) ground state of the benzene anion. The process of nuclear wavepacket relaxation appears to be accompanied by intramolecular vibrational redistribution (IVR) whereby the initially vibrationally selective electron attachment at higher energies within the resonance is converted to vibrational states with many overtones and combinations excited.…”
Section: Boomerang Structure Of the π * E 2u Resonance At 115 Evmentioning
confidence: 99%