| DOI | Trouver le DOI : https://doi.org/10.1063/1.1411999 |
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| Auteur | Rechercher : Zgierski, Marek1 |
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| Affiliation | - Conseil national de recherches du Canada. Institut Steacie des sciences moléculaires du CNRC
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| Format | Texte, Article |
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| Sujet | coupled cluster calculations; density functional theory; HF calculations; isomerism; organic compounds; photochromism |
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| Résumé | It is shown that the direct precursor for the formation of a photochrome in Schiff bases is a "twisted" geometry S1 state of a keto tautomer in which the O[centered ellipsis]N�H hydrogen bond is broken. In photochromic Schiff bases this state is close in energy to the pipi* state of the cis-ketone obtained from the initially optically excited enol species by an ultrafast excited-state proton transfer, in particular, in N-salicylidene-alpha-methylbenzylamine (SMB), it lies within 1 kcal/mol from the pipi* state of cis-ketone and ~16 kcal/mol below the initial pipi* state of enol. The excited-state proton transfer in SMB is predicted to take ~15 fs and to be nearly barrierless. It is also shown that the initial pipi* state of enol can decay via competing route to a twisted geometry nNpi* state of enol with the energy ~20 kcal/mol below that state. |
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| Date de publication | 2001-11-08 |
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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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| Numéro NPARC | 12339026 |
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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 | 67dc023d-b8a3-4947-a142-34bb98ec8f6f |
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| Enregistrement créé | 2009-09-11 |
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| Enregistrement modifié | 2020-03-27 |
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