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Updated: May 11, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Vertical transition energies vs. absorption maxima: illustration with the UV absorption spectrum of ethylene
Benjamin Lasorne1, Joaquim Jornet-Somoza, Hans-Dieter Meyer
1Institut Charles Gerhardt Montpellier, Université Montpellier 2, CC 15001, Place Eugène Bataillon, 34095 Montpellier, France.
Abstract:
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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