TD-DFT Analysis of the Dissymmetry Factor in Camphor

• Autor(a) principal: Sousa, Iran da L.
• Data de Publicação: 2020
• Outros Autores: Heerdt, Gabriel, Ximenes, Valdecir F. [UNESP], Souza, Aguinaldo R. de [UNESP], Morgon, Nelson H.
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Institucional da UNESP
• Texto Completo: http://dx.doi.org/10.21577/0103-5053.20190226; http://hdl.handle.net/11449/195185
• topic: S-camphor; L-tryptophan; UV-Vis; ECD; g-factor; TD-DFT

The fact that the dissymmetry factor (g-factor) of camphor is large has been known for decades, and the interpretation of the observed data has also been known for a long time. However, due to the ability of quantum chemical methods to describe chiroptical phenomena more appropriately, additional approaches based on these methods have been successful employed. The g-factor present in S-camphor and L-tryptophan have been investigated by UV-Vis and electronic circular dichroism (ECD) spectroscopies of the n -> pi* electronic transition. Time-dependent density functional theory (TD-DFT) calculations at CAM-B3LYP/6-311++G(3df,2p)//B3LYP/6-311++G(2d,p) level of theory including Grimme's dispersion effects have been performed. The solvent effect was added using solvation model based on density (SMD) approach in solvation environment. The results permit insights into the ground and excited states electronic properties associated with the g-factor. The theoretical spectra showed good similarity with the experimental ones. The theoretical ECD of camphor was found at 282 nm, whereas the experimental shows its maximum at 290 nm. Regarding the maximum value of the molar absorptivity coefficient, the theoretical and experimental values were 16.2 and 30.2 M-1 cm(-1),respectively. The same concordance was obtained for g-factor, as follows: -0.0445 and -0.0886, for experimental and theoretical results, respectively.