Conformational instability of the lowest triplet state of the benzene nucleus. I. The unsubstituted molecule

Buma, W. J.; Waals, J.H. van der; Hemert, Marc C. van

doi:10.1063/1.458809

Cited by 29 publications

(18 citation statements)

References 62 publications

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“…The threshold behavior for the triplet states is complicated by the distortion of the lowest energy conformation to a lower symmetry. 24 The excitation energy between the triplet states is 0.2 eV larger than the peak separations of the experimental electron impact spectrum but the excitation energy at the triplet geometry cannot easily be discerned from the threshold behavior of the electron impact spectrum. The restricted active space, however, could lead to errors of this order, which is still comparable to the more extensive Cl calculations in the literature.…”

Section: Resultsmentioning

confidence: 89%

Assignment of the spectra of protein radicals in cytochrome c peroxidase

Krauß¹,

Garmer²

1993

J. Phys. Chem.

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In oxidized cytochrome c peroxidase a peak at 570 nm has been attributed to an intermediate tryptophan free radical of indeterminate protonation state. Ab initio calculations of the spectra of the neutral and cationic free radicals of the indole side chain of tryptophan are used to assign the absorption spectra to the neutral radical. Earlier assignment attempts were confused by the large blue shift in water of the in vacuo transition. The relevant calculated transitions of both the neutral and cationic indole radicals, in fact, shift substantially to the blue in aqueous solution. The theoretical cation spectra do not agree with the experimental spectra and suggest a tautomeric form is observed. Calculations of the valence singlet and triplet excited states of benzene and triplet states of indole are also presented to support the ab initio calculations of the indole radical. Spin densities are calculated for both neutral and cation radicals. The small spin density on nitrogen found for the cation is more in agreement with experimental ENDOR data. The visible and ENDOR data suggest different states of protonation and cannot be reconciled to the electronic properties of the ground-state radical tautomers.

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Section: Resultsmentioning

confidence: 89%

Assignment of the spectra of protein radicals in cytochrome c peroxidase

Krauß¹,

Garmer²

1993

J. Phys. Chem.

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“…In their paper, amongst the local minima, there were two very close in energy, called quinoidal and anti-quinoidal, with D 2h symmetry. Their discussion extended experimental and theoretical work spanning decades by Van der Waals and coworkers [38,43,45,46], Robinson and coworkers [39,42], and many others [14,40,41,44]. The existence of multiple conformations of the triplet state of organic molecules is an extremely interesting phenomenon.…”

Section: Fully Benzenoid Hydrocarbonsmentioning

confidence: 93%

Geometry and bonding in the ground and lowest triplet state of D6h symmetric crenellated edged C6[3m(m−1)+1]H6(2m−1) (m=2,…,6) graphene hydrocarbon molecules

Philpott

2009

Chemical Physics

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“…[39][40][41]43 Here, we obtained three stationary configurations-an atiquinoid, a quinoid and a boatlike, C s configuration. [39][40][41]43 Here, we obtained three stationary configurations-an atiquinoid, a quinoid and a boatlike, C s configuration.…”

Section: B the T 1 Statementioning

confidence: 93%

“…[29][30][31][32][33][34][35][36][37][38][39][40][41][42] This distortion is probably due to vibronic coupling with modes of e 2g symmetry, especially 8 and 9 . [29][30][31][32][33][34][35][36][37][38][39][40][41][42] This distortion is probably due to vibronic coupling with modes of e 2g symmetry, especially 8 and 9 .…”

Section: B the T 1 Statementioning

confidence: 99%

A phase-space approach to the T1⇝S radiationless decay in benzene: The effect of deuteration

Zamstein

Kallush

Segev

2005

The Journal of Chemical Physics

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The influence of full deuteration on the T1 right arrow-wavy S0 intersystem crossing in benzene is studied by a phase space approach. A full treatment of all the vibrational modes in the molecule leads to a ratio of the rate between the two isotopomers which is very close to the experimental value. Several aspects of the results are compared to previous estimates, and the effects of anharmonicity on the rates and accepting modes are examined. This first successful application of the method to a real physical system encourages the possibility of establishing a routine procedure for simple calculations of transition rates even for relatively large molecules.

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Conformational instability of the lowest triplet state of the benzene nucleus. I. The unsubstituted molecule

Abstract: Conformational instability of the lowest triplet state of the benzene nucleus: I. The unsubstituted molecule van der Waals, J.H.; van Hemert, M.C.; Buma, W.J.

Cited by 29 publications

References 62 publications

Assignment of the spectra of protein radicals in cytochrome c peroxidase

Assignment of the spectra of protein radicals in cytochrome c peroxidase

Geometry and bonding in the ground and lowest triplet state of D6h symmetric crenellated edged C6[3m(m−1)+1]H6(2m−1) (m=2,…,6) graphene hydrocarbon molecules

A phase-space approach to the T1⇝S radiationless decay in benzene: The effect of deuteration

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