Ab initio electronic absorption spectra of para-nitroaniline in different solvents : Intramolecular charge transfer effects
© 2024 Wiley Periodicals LLC.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - (2024) vom: 30. Aug. |
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| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2024
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Para–Nitroaniline electronic absorption spectra explicit and implicit solvent models intramolecular charge transfer (ICT) second band second‐order algebraic diagrammatic construction ADC(2) |
| Zusammenfassung: | © 2024 Wiley Periodicals LLC. Intramolecular charge transfer (ICT) effects of para-nitroaniline (pNA) in eight solvents (cyclohexane, toluene, acetic acid, dichloroethane, acetone, acetonitrile, dimethylsulfoxide, and water) are investigated extensively. The second-order algebraic diagrammatic construction, ADC(2), ab initio wave function is employed with the COSMO implicit and discrete multiscale solvation methods. We found a decreasing amine group torsion angle with increased solvent polarity and a linear correlation between the polarity and ADC(2) transition energies. The first absorption band involves π → π* transitions with ICT from the amine and the benzene ring to the nitro group, increased by 4%-11% for different solvation models of water compared to the vacuum. A second band of pNA is characterized for the first time. This band is primarily a local excitation on the nitro group, including some ICT from the amine group to the benzene ring that decreases with the solvent polarity. For cyclohexane, the COSMO implicit solvent model shows the best agreement with the experiment, while the explicit model has the best agreement for water |
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| Beschreibung: | Date Revised 30.08.2024 published: Print-Electronic Citation Status Publisher |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.27493 |