TD-DFT Analysis of the Dissymmetry Factor in Camphor
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Data
2020-03-01
Autores
Sousa, Iran da L.
Heerdt, Gabriel
Ximenes, Valdecir F. [UNESP]
Souza, Aguinaldo R. de [UNESP]
Morgon, Nelson H.
Título da Revista
ISSN da Revista
Título de Volume
Editor
Soc Brasileira Quimica
Resumo
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.
Descrição
Palavras-chave
S-camphor, L-tryptophan, UV-Vis, ECD, g-factor, TD-DFT
Como citar
Journal Of The Brazilian Chemical Society. Sao Paulo: Soc Brasileira Quimica, v. 31, n. 3, p. 613-618, 2020.