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Assessment of franck–condon methods for computing vibrationally broadened UV–vis absorption spectra of flavin derivatives : riboflavin, roseoflavin, and 5-thioflavin
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Karasulu, Bora, Götze, Jan Philipp and Thiel, Walter (2014) Assessment of franck–condon methods for computing vibrationally broadened UV–vis absorption spectra of flavin derivatives : riboflavin, roseoflavin, and 5-thioflavin. Journal of Chemical Theory and Computation, 10 (12). pp. 5549-5566. doi:10.1021/ct500830a ISSN 1549-9618.
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Official URL: http://dx.doi.org/10.1021/ct500830a
Abstract
We address the performance of the vertical and adiabatic Franck–Condon (VFC/AFC) approaches combined with time-independent or time-dependent (TI/TD) formalisms in simulating the one-photon absorption spectra of three flavin compounds with distinct structural features. Calculations were done in the gas phase and in two solvents (water, benzene) for which experimental reference measurements are available. We utilized the independent mode displaced harmonic oscillator model without or with frequency alteration (IMDHO/IMDHO-FA) and also accounted for Duschinsky mixing effects. In the initial validation on the first excited singlet state of riboflavin, the range-separated functionals, CAM-B3LYP and ωB97xD, showed the best performance, but B3LYP also gave a good compromise between peak positions and spectral topology. Large basis sets were not mandatory to obtain high-quality spectra for the selected systems. The presence of a symmetry plane facilitated the computation of vibrationally broadened spectra, since different FC variants yield similar results and the harmonic approximation holds rather well. Compared with the AFC approach, the VFC approach performed equally well or even better for all three flavins while offering several advantages, such as avoiding error-prone geometry optimization procedures on excited-state surfaces. We also explored the advantages of curvilinear displacements and of a Duschinsky treatment for the AFC spectra in cases when a rotatable group is present on the chromophore. Taken together, our findings indicate that the combination of the VFC approach with the TD formalism and the IMDHO-FA model offers the best overall performance.
Item Type: | Journal Article | ||||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||
Journal or Publication Title: | Journal of Chemical Theory and Computation | ||||||
Publisher: | American Chemical Society | ||||||
ISSN: | 1549-9618 | ||||||
Official Date: | December 2014 | ||||||
Dates: |
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Volume: | 10 | ||||||
Number: | 12 | ||||||
Page Range: | pp. 5549-5566 | ||||||
DOI: | 10.1021/ct500830a | ||||||
Status: | Peer Reviewed | ||||||
Publication Status: | Published | ||||||
Access rights to Published version: | Restricted or Subscription Access |
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