| Autre titre | The ultrafast vacuum ultraviolet (VUV) Rydberg state dynamics of cyclic ethers reflects ring strain |
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| DOI | Trouver le DOI : https://doi.org/10.1039/D0CP04292G |
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| Auteur | Rechercher : Röder, AnjaIdentifiant ORCID : https://orcid.org/0000-0001-9291-347X; Rechercher : Skov, Anders B.; Rechercher : Boguslavskiy, Andrey E.1; Rechercher : Lausten, Rune1; Rechercher : Stolow, AlbertIdentifiant ORCID : https://orcid.org/0000-0002-8447-3678 |
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| Affiliation | - Conseil national de recherches du Canada. Technologies de sécurité et de rupture
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| Format | Texte, Article |
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| Résumé | The vacuum ultraviolet (VUV) absorption spectra of cyclic ethers consist primarily of Rydberg ← n transitions. By studying three cyclic ethers of varying ring size (tetrahydropyran, tetrahydrofuran and trimethylene oxide, n = 6–4), we investigated the influence of ring size on the VUV excited-state dynamics of the 3d Rydberg manifold using time-resolved photoelectron spectroscopy (TRPES), time-resolved mass spectroscopy (TRMS) and ab initio electronic structure calculations. Whereas neither the electronic characters nor the term energies of the excited-states are substantially modified when the ring-size is reduced from n = 6 to 5 to 4, the excited-state lifetimes concomitantly decrease five-fold. TRPES and TRMS allow us to attribute the observed dynamics to a Rydberg cascade from the initially excited d-Rydberg manifold via the p-Rydberg manifold to the s-Rydberg state. Cuts through potential energy surfaces along the C–O bond reveal that a nσ* state crossing brings the s-Rydberg state along a path to the ring-opened ground state. The observed difference in excited-state lifetimes is attributed to an increasing slope along the repulsive C–O bond coordinate as ring size decreases. |
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| Date de publication | 2020-10-27 |
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| Maison d’édition | Royal Society of Chemistry |
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| Dans | |
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| Langue | anglais |
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| Publications évaluées par des pairs | Oui |
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| Exporter la notice | Exporter en format RIS |
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| Signaler une correction | Signaler une correction (s'ouvre dans un nouvel onglet) |
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| Identificateur de l’enregistrement | 02863ef9-5bfd-443d-9c03-4ad55a3be971 |
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| Enregistrement créé | 2021-05-11 |
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| Enregistrement modifié | 2021-05-13 |
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