| DOI | Resolve DOI: https://doi.org/10.1063/1.1411999 |
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| Author | Search for: Zgierski, Marek1 |
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| Affiliation | - National Research Council Canada. NRC Steacie Institute for Molecular Sciences
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| Format | Text, Article |
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| Subject | coupled cluster calculations; density functional theory; HF calculations; isomerism; organic compounds; photochromism |
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| Abstract | 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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| Publication date | 2001-11-08 |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| NPARC number | 12339026 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | 67dc023d-b8a3-4947-a142-34bb98ec8f6f |
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| Record created | 2009-09-11 |
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| Record modified | 2020-03-27 |
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