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- Title
Thermal Fluctuations in Conjugation and their Effect on Calculated Excitation Energies: A Case Study on the Astaxanthin Carotenoid.
- Authors
Wang, Jun; Durbeej, Bo
- Abstract
A popular approach to the calculation of molecular excitation energies is to consider only equilibrium geometries and neglect the effects of thermal motion. Although this static approach is sensible for molecules with distinct potential‐energy minima, its adequacy relative to dynamical approaches appears not to have been thoroughly tested. Here, we report a case study investigating how thermal motion accounted for by molecular dynamics simulations influences the optically bright state of astaxanthin, a carotenoid of broad photobiological interest that features 13 conjugated double bonds. Employing several different density functional methods, it is shown that thermal fluctuations in the conjugation result in the Boltzmann‐weighted average excitation energies for this state being shifted by up to 0.05 eV relative to those obtained from purely static calculations. Accordingly, it is concluded that the effects of thermal motion on excitation energies of conjugated systems can be quite large even for molecules with distinct potential‐energy minima.
- Subjects
MOLECULAR dynamics; ASTAXANTHIN; DENSITY functionals; CONJUGATED systems; DOUBLE bonds
- Publication
ChemPhotoChem, 2022, Vol 6, Issue 1, p1
- ISSN
2367-0932
- Publication type
Article
- DOI
10.1002/cptc.202100178