Abstract
We report a systematic computational investigation on the electronic and optical properties of the principal chromophores found in bacterial cellulose (BC). In particular, we focus on the three chromophoric leading structures that were isolated from aged BC (1) 2,5-dihydroxy-[1,4]benzoquinone (2) 5,8-dihydroxy-[1,4]naphthoquinone and (3) 2,5-dihydroxyacetophenone. For the isolated molecules we performed all-electrons density functional theory (DFT) and time dependent DFT calculations with a localized Gaussian basis set and the hybrid exchange correlation functional B3LYP. We quantified key molecular properties relevant as electron affinities, ionization energies, quasi-particle energy gaps, optical absorption spectra, and exciton binding energies. We address moreover the impact of the solvent on the optical properties of the above systems using starting configurations obtained after classical molecular dynamics simulations in water. Our results could be of importance to comprehend the mechanisms underlying the processes of degradation of BC, which are of fundamental relevance for cultural heritage applications.
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Acknowledgments
The authors acknowledge the use of computational resources of CRS4 with special thanks to the high performance computing staffs. GC and RC acknowledge partial financial support from IDEA-AISBL Bruxelles. GC also acknowledges partial financial support from Progetto biennale d’Ateneo UniCa/FdS/RAS(Legge Regionale 07/08/2007 Annualità 2016) “Multiphysics theoretical approach to Thermoelectricity”. The authors thank A. Mosca Conte for introducing the topic of research and initial discussions.
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The absorption spectrum for the molecules expressed in oscillatory strength (Figs. S1–S4). Comparison between bond distance of the molecules after classical geometry optimization in vacuum and for the solvated conformer obtained from MD simulation in water (Tables S1–S4). In Table S5, detailed comparison among the absorption spectra of the three most probable conformers of molecule C extracted from MD simulations in water. (DOCX 2341 kb)
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Kumar, A., Cardia, R. & Cappellini, G. Electronic and optical properties of chromophores from bacterial cellulose. Cellulose 25, 2191–2203 (2018). https://doi.org/10.1007/s10570-018-1728-0
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DOI: https://doi.org/10.1007/s10570-018-1728-0