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Article Dans Une Revue Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy [1994-...] Année : 2014

Vertical transition energies vs. absorption maxima: Illustration with the UV absorption spectrum of ethylene

Résumé

We revisit the validity of making a direct comparison between measured absorption maxima and computed vertical transition energies within 0.1 eV to calibrate an excited-state level of theory. This is illustrated on the UV absorption spectrum of ethylene for which the usual experimental values of 7.66 eV (V ← N) and 7.11 eV (R(3s) ← N) cannot be compared directly to the results of electronic structure calculations for two very different reasons. After validation of our level of theory against experimental data, a new experimental reference of 7.28 eV is suggested for benchmarking the Rydberg state, and the often-cited average transition energy (7.80 eV) is confirmed as a safer estimate for the valence state.
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hal-00905569 , version 1 (18-11-2013)

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Benjamin Lasorne, Joaquim Jornet-Somoza, Hans-Dieter Meyer, David Lauvergnat, Michael A. Robb, et al.. Vertical transition energies vs. absorption maxima: Illustration with the UV absorption spectrum of ethylene. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy [1994-..], 2014, 119, pp.52. ⟨10.1016/j.saa.2013.04.078⟩. ⟨hal-00905569⟩
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