دورية أكاديمية
Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state
| العنوان: | Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state |
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| المؤلفون: | Chatterjee, G., Jha, A., Blanco-Gonzalez, A., Tiwari, V., Manathunga, M., Duan, H., Tellkamp, F., Prokhorenko, V., Ferré, N., Dasgupta, J., Olivucci, M., Miller, R. |
| المصدر: | Chemical Science |
| سنة النشر: | 2022 |
| المجموعة: | Max Planck Society: MPG.PuRe |
| الوصف: | The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Here, we demonstrate that out-of-plane torsional deformation and vibrational excitation of stretching motions in the electronic ground state modulate the charge-density distribution in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change, visualised by transient absorption spectroscopy with a mid-infrared pump and a visible probe, is mechanistically resolved by ab initio molecular dynamics simulations. Mapping the potential energy landscape attributes the observed charge-coupled coherent nuclear motions to the population of the initial segment of a double-bond isomerization channel, also seen in biological molecules. Our results illustrate the pivotal role of pre-twisted molecular geometries in enhancing the transfer of vibrational energy to specific molecular modes, prior to thermal redistribution. This motivates the search for synthetic strategies towards achieving potentially new infrared-mediated chemistry. |
| نوع الوثيقة: | article in journal/newspaper |
| وصف الملف: | application/pdf |
| اللغة: | English |
| العلاقة: | http://hdl.handle.net/21.11116/0000-000A-C3B6-CTest; http://hdl.handle.net/21.11116/0000-000A-DEB0-5Test; http://hdl.handle.net/21.11116/0000-000A-DEB1-4Test |
| الإتاحة: | https://doi.org/10.1039/D2SC02133ATest http://hdl.handle.net/21.11116/0000-000A-C3B6-CTest http://hdl.handle.net/21.11116/0000-000A-DEB0-5Test http://hdl.handle.net/21.11116/0000-000A-DEB1-4Test |
| حقوق: | info:eu-repo/semantics/openAccess ; http://creativecommons.org/licenses/by-nc/3.0Test/ |
| رقم الانضمام: | edsbas.F8500B18 |
| قاعدة البيانات: | BASE |
| الوصف غير متاح. |