Unbiased Determination of Absolute Configurations by vis-à-vis Comparison of Experimental and Simulated Spectra: The Challenging Case of Diplopyrone
| Autor: | Fuse, M., Mazzeo, G., Longhi, G., Abbate, S., Masi, M., Evidente, A., Puzzarini, C., Barone, V., Fuse', Marco |
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| Přispěvatelé: | Fuse', M., Mazzeo, G., Longhi, G., Abbate, S., Masi, M., Evidente, A., Puzzarini, C., Barone, V., Fusè, Marco, Mazzeo, Giuseppe, Longhi, Giovanna, Abbate, Sergio, Masi, Marco, Evidente, Antonio, Puzzarini, Cristina, Barone, Vincenzo, Fuse M., Mazzeo G., Longhi G., Abbate S., Masi M., Evidente A., Puzzarini C., Barone V. |
| Rok vydání: | 2019 |
| Předmět: |
chirality
Infrared spectroscopy 010402 general chemistry 01 natural sciences Spectral line Software 0103 physical sciences Dispersion (optics) Materials Chemistry Statistical physics Physical and Theoretical Chemistry computational spectroscopy Settore CHIM/02 - Chimica Fisica Physics 010304 chemical physics Basis (linear algebra) business.industry Anharmonicity 0104 chemical sciences Surfaces Coatings and Films VCD spectroscopy IR spectroscopy Vibrational circular dichroism Perturbation theory (quantum mechanics) business |
| Zdroj: | The Journal of Physical Chemistry B. 123:9230-9237 |
| ISSN: | 1520-5207 1520-6106 |
| Popis: | A new experimental-computational strategy for the determination of the absolute configuration (AC) of complex chiral molecules is proposed by combining diverse experimental spectroscopies with quantum-mechanical simulations well beyond the current computational practice. Key features are the conformer search and relative stability evaluation performed by a new stochastic two-level tool followed by a vis-à-vis comparison of experimental and computed spectra without any ad hoc adjustment. The entire computational procedure is embedded in the user-friendly VMS software, and its reliability is granted by the inclusion of mechanic/electric/magnetic anharmonicity as well as ro-vibrational and vibronic couplings by means of generalized perturbation theory in conjunction with double-hybrid functionals combined with empirical dispersion contributions and suitable basis sets. To test and validate the new approach, the puzzling case of diplopyrone, a fungal phytotoxic metabolite, has been chosen: the close match between new experimental and simulated infrared absorption and vibrational circular dichroism spectra has led to the unbiased evaluation of its AC. A new experimental-computational strategy for the determination of the absolute configuration (AC) of complex chiral molecules is proposed by combining diverse experimental spectroscopies with quantum-mechanical simulations well beyond the current computational practice. Key features are the conformer search and relative stability evaluation performed by a new stochastic two-level tool followed by a vis-à-vis comparison of experimental and computed spectra without any ad hoc adjustment. The entire computational procedure is embedded in the user-friendly VMS software, and its reliability is granted by the inclusion of mechanic/electric/magnetic anharmonicity as well as ro-vibrational and vibronic couplings by means of generalized perturbation theory in conjunction with double-hybrid functionals combined with empirical dispersion contributions and suitable basis sets. To test and validate the new approach, the puzzling case of diplopyrone, a fungal phytotoxic metabolite, has been chosen: the close match between new experimental and simulated infrared absorption and vibrational circular dichroism spectra has led to the unbiased evaluation of its AC. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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