Improving the Description of the Optical Properties of Carotenoids by Tuning the Long-Range Corrected Functionals

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• 作者：Igo T. Lima ; Andriele da S. Prado ; João B. L. Martins ; Pedro Henrique de Oliveira Neto ; Artemis M. Ceschin ; Wiliam F. da Cunha ; Demétrio A. da Silva Filho
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：July 14, 2016
• 年：2016
• 卷：120
• 期：27
• 页码：4944-4950
• 全文大小：416K
• 年卷期：0
• ISSN：1520-5215

文摘

In this work we use gap-fitting procedure to tune the long-range corrected functionals and accurately investigate the electronic and optical properties of the five main molecules composing Buriti oil (extracted from Mauritia flexuosa L.) in the framework of density functional theory (DFT) and time-dependent (TD) DFT. The characteristic length (1/ω) was observed to be entirely system dependent, though we concluded that its determination is of fundamental importance to rescue geometrical, electronic, and optical properties with accuracy. We demonstrate that our approach of tuning characteristic length for each system resulted in an absorbance spectra in better experimental agreement when compared to the traditional methodology. Therefore, this study indicates that the tuning of the range-separation parameter is crucial to improve the description of the optical properties of conjugated molecules when TDDFT is used. For example, the wavelength of maximum absorption, λ<sub>maxsub>, for the phytofluene, obtained using B3LYP, is 381 nm, while using the gap-fitting procedure for the tuned-LC-BLYP the estimated λ<sub>maxsub> changed to 358 nm. The latter estimate is in better agreement with the experimental value of 350 nm.