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Excitation, Ionization, and Fragmentation of Chiral Molecules in Asymmetric Microenvironments: a Mass-Resolved R2PI Spectroscopic Study (Articolo in rivista)

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Excitation, Ionization, and Fragmentation of Chiral Molecules in Asymmetric Microenvironments: a Mass-Resolved R2PI Spectroscopic Study (Articolo in rivista) (literal)

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Alternative label

Piccirillo S. 1; Rondino F. 2; Catone D. 2; Giardini Guidoni A. 2,3; Paladini A. 2; Tacconi M. 2; Satta M. 3; Speranza M.4 (2005)
Excitation, Ionization, and Fragmentation of Chiral Molecules in Asymmetric Microenvironments: a Mass-Resolved R2PI Spectroscopic Study
in The journal of physical chemistry. A; American Chemical Society, Washington (Stati Uniti d'America)
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Piccirillo S. 1; Rondino F. 2; Catone D. 2; Giardini Guidoni A. 2,3; Paladini A. 2; Tacconi M. 2; Satta M. 3; Speranza M.4 (literal)

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1. Dipartimento di Scienze e Tecnologie Chimiche, Univ. Degli Studi Roma Tor Vergata, Roma, Italy; 2. Dipartimento di Chimica, Univ. Degli Studi Roma La Sapienza, Roma, Italy; 3. CNR-IMIP, (sezione Istituto Materiali Speciali), Tito Scalo (Pz), Italy; 4. Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente AttiVe, Univ. degli Studi Roma La Sapienza, Roma, Italy (literal)

Titolo

Excitation, Ionization, and Fragmentation of Chiral Molecules in Asymmetric Microenvironments: a Mass-Resolved R2PI Spectroscopic Study (literal)

Abstract

One- and two-color, mass selected R2PI spectra of the S1 ? S0 transitions in the bare (R)-(+)-1-phenyl-1-propanol and its complexes with bidentate solvent molecules, like the (R)-(-)- and (S)-(+)-3-hydroxytetrahydrofuran enantiomers, have been recorded after a supersonic molecular beam expansion. The one-color R2PI excitation spectra of the diastereomeric complexes are characterized by three main peaks, one red-shifted and the other two blue-shifted relative to the band origin of the most stable anti conformer of the bare chromophore. The opposite direction of these spectral shifts is ascribed to the occurrence of three different hydrogen bonded isomeric structures for each individual complex, while their different magnitude depends on the configuration of the bidentate solvent molecule as well as its specific hydrogen bond interaction center, whether the ethereal oxygen atom or the hydroxyl group. The same factors play a major role in determining the magnitude of the phenomenological activation barriers for the loss of an ethyl radical from the ionized diastereomeric complexes. (literal)

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