Spectroscopic Properties of Lumiflavin: A Quantum Chemical Study

Rajiv Kumar Kar, Veniamin A. Borin, Yonghong Ding, Jörg Matysik, Igor Schapiro*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

In this work, the electronic structure and spectroscopic properties of lumiflavin are calculated using various quantum chemical methods. The excitation energies for ten singlet and triplet states as well as the analysis of the electron density difference are assessed using various wave function-based methods and density functionals. The relative order of singlet and triplet excited states is established on the basis of the coupled cluster method CC2. We find that at least seven singlet excited states are required to assign all peaks in the UV/Vis spectrum. In addition, we have studied the solvatochromic effect on the excitation energies and found differential effects except for the first bright excited state. Vibrational frequencies as well as IR, Raman and resonance Raman intensities are simulated and compared to their experimental counterparts. We have assigned peaks, assessed the effect of anharmonicity, and confirmed the previous assignments in case of the most intense transitions. Finally, we have studied the NMR shieldings and established the effect of the solvent polarity. The present study provides data for lumiflavin in the gas phase and in implicit solvent model that can be used as a reference for the protein-embedded flavin simulations and assignment of experimental spectra.

Original languageAmerican English
Pages (from-to)662-674
Number of pages13
JournalPhotochemistry and Photobiology
Volume95
Issue number2
DOIs
StatePublished - 1 Mar 2019

Bibliographical note

Publisher Copyright:
© 2018 The American Society of Photobiology

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