Vibronic interaction in the lower electronic states of benzene

Waals, J.H. van der; Berghuis, A.M.; Groot, M.S. de

doi:10.1080/00268977100101671

Cited by 46 publications

(4 citation statements)

References 26 publications

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“…Detailed calculations on benzene have shown [22] that even a weakly anisotropic crystal field will act on the pseudo Jahn-Teller unstable molecule and lead to a markedly non-hexagonal spin distribution, as observed during an electron spin resonance experiment.…”

Section: Discussionmentioning

confidence: 92%

Paramagnetic resonance of phosphorescent tetramethylpyrazine

et al. 1975

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Electron paramagnetic resonance spectra have been obtained of tetramethylpyrazine in its lowest (~r~r*) triplet state in several rigid matrices. Some unusual observations were made :(1) In a durene crystal host the in-plane zero-field principal axes are not parallel to the molecular symmetry axes.(2) In rigid glass solution the zero-field parameters are strongly dependent on solvent polarity. Both effects are discussed in terms of pseudo Jahn-Teller interaction in conjunction with a crystal-field influence.In a durene matrix the zero-field parameters are z~= 0"0457 + 0.0002 cm -1, Y= 0"0187 _+ 0'0002 cm-*, X = -0"0641 _+ 0.0003 cm -1. The relatively small value of D = -~X', as compared with that of the corresponding aromatic hydrocarbon, probably results from vibronic mixing of the lowest ~TrTr* with the near-by ~nzr* state.Hyperfine structure was observed during measurements at 1"95 K ; it is in agreement with the 7r~r* character of the lowest triplet state and is due to coupling between the unpaired electrons and protons in the non-rotating methyl groups.

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Section: Discussionmentioning

confidence: 92%

Paramagnetic resonance of phosphorescent tetramethylpyrazine

et al. 1975

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“…For the calculations, the authors 341 employed a two-mode PJT model. 350,351 The JT coupling parameters used to fit the calculated spectral lines to the observed ones are given in Table 16.…”

Section: The Benzene Family Molecular and Radical Cation And Anion Sy...mentioning

confidence: 99%

Modern Aspects of the Jahn−Teller Effect Theory and Applications To Molecular Problems

2001

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“…A very similar form of pseudo-JT dynamic coupling was presented in an excellent series of papers by van der Waals and co-workers. [50][51][52] They developed a model which described the coupling between the 3 B 1u and 3 E 1u electronic states of neutral benzene via two e 2g vibrational modes. Their coupling case is, in essence, very similar to the one we are considering, the major differences being the relative ordering and the angular momenta of the electronic states.…”

Section: A the Pseudo-jahn-teller Effectmentioning

confidence: 99%

The observation of strong pseudo-Jahn–Teller activity in the benzene cation B̃ 2E2g state

Goode

Hofstein

Johnson

1997

The Journal of Chemical Physics

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Articles you may be interested in K selection in one-photon mass-analyzed threshold ionization of C H 3 I and C D 3 I to the X ̃ E 3 ∕ 2 2 state cations J. Chem. Phys. 128, 044310 (2008); 10.1063/1.2823032 Diradicals, antiaromaticity, and the pseudo-Jahn-Teller effect: Electronic and rovibronic structures of the cyclopentadienyl cationThe Jahn-Teller effect in the lower electronic states of benzene cation. II. Vibrational analysis and coupling constants of the B̃ 2 E 2g state Photoinduced Rydberg ionization ͑PIRI͒ spectroscopy has been applied to the problem of recording vibrationally resolved spectra of the dipole-forbidden B 2 E 2g ←X 2 E 1g transition of C 6 H 6 ϩ and C 6 D 6 ϩ . PIRI spectra of the B state have been recorded via a number of vibrational states of the ionic ground state. A combination of Herzberg-Teller and pseudo-Jahn-Teller vibronic coupling between the B state and a close lying C state were used to explain the complex B state vibrational structure. The two pseudo-Jahn-Teller vibrational modes, 16 and 17 , were both found to be active in the PIRI spectra. In addition, evidence for a strong pseudo-Jahn-Teller interaction within each of these modes was found. The perturbed vibronic bands resulting from this pseudo-Jahn-Teller activity were successfully modeled using a two-mode pseudo-Jahn-Teller vibronic coupling model. Using a combination of the spectral results and the pseudo-Jahn-Teller calculations, we were able to generate absolute vibronic symmetry assignments for many of the lower B state vibrational levels, from which vibrational assignments were made. The calculations also produced unperturbed vibrational frequencies for both pseudo-Jahn-Teller active modes along with values for their respective linear coupling constants.

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Vibronic interaction in the lower electronic states of benzene

Cited by 46 publications

References 26 publications

Paramagnetic resonance of phosphorescent tetramethylpyrazine

Paramagnetic resonance of phosphorescent tetramethylpyrazine

Modern Aspects of the Jahn−Teller Effect Theory and Applications To Molecular Problems

The observation of strong pseudo-Jahn–Teller activity in the benzene cation B̃ 2E2g state

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