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Analysis of lowest energy transitions at TD-DFT of pyrene in vacuum and solvent

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Abstract

Polycyclic aromatic hydrocarbons are present in interstellar medium and trapped in water ice. Among these compounds, pyrene has a controversial theoretical excitation spectrum. We carried out time-dependent density functional theory, including the long-range correction functionals, with the aim to help to understand the inversion of the first two UV bands of lower energies. The pyrene molecule was optimized at TD-DFT functionals with Def2svp basis set. The spectrum of pyrene molecule was calculated using implicit and explicit solvent models. The explicit solvent effect was studied, including a cluster of 51 water molecules. The implicit solvent PCM model was used with water and benzene as solvents. CAM-B3LYP and ωB97XD give correct band positions and the ω parameter was also optimized. NBO and frontier molecular orbitals were used to study the UV band inversion.

Analysis of frontier orbitals involved in the lowest energy transitions at TD-DFT of pyrene

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Acknowledgments

The authors are indebted to the financial support of FAPDF, CNPq, and CAPES and the computational support of CENAPAD/SP and UnB/FINEP Institute of Chemistry Computational Centre.

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  1. Chemistry Institute, University of Brasilia, Brasília, DF, 70910-900, Brazil

    Eric L. Graef & João B. L. Martins

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  1. Eric L. Graef
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Correspondence to João B. L. Martins.

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Graef, E.L., Martins, J.B.L. Analysis of lowest energy transitions at TD-DFT of pyrene in vacuum and solvent. J Mol Model 25, 183 (2019). https://doi.org/10.1007/s00894-019-4065-9

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