Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/10654
Title: Matrix-Isolated Diglycolic Anhydride: Vibrational Spectra and Photochemical Reactivity
Authors: Jarmelo, S. 
Reva, I. D. 
Lapinski, L. 
Nowak, M. J. 
Fausto, R. 
Issue Date: 6-Nov-2008
Publisher: American Chemical Society
Citation: The Journal of Physical Chemistry A. 112:44 (2008) 11178-11189
Abstract: The structure of diglycolic anhydride (1,4-dioxane-2,6-dione; DGAn) isolated in a low-temperature argon matrix at 10 K was studied by means of FTIR spectroscopy. Interpretation of the experimental vibrational spectrum was assisted by theoretical calculations at the DFT(B3LYP)/aug-cc-pVTZ level. The optimized structure of the isolated DGAn molecule adopts an envelope conformation, which was found to resemble closely the structure of DGAn in a crystal. The UV-induced (λ > 240 nm) photolysis of the matrix-isolated compound was also investigated. In order to identify the main species resulting from irradiation of the monomeric DGAn, a comparison between the DFT(B3LYP)/aug-cc-pVTZ calculated spectra of the putative products and the experimental data was carried out. The observed photoproducts can be explained by a model involving four channels: (a) 1,3-dioxolan-4-one + CO; (b) CO2 + CO + oxirane; (c) formaldehyde + ketene + CO2; (d) oxiran-2-one + oxiran-2-one. As a whole, the experiments indicated that the C−O−C bridge, connecting the two CO groups, is the most reactive fragment in the molecule excited with UV light. This observation was confirmed by the natural bond orbital (NBO) analysis revealing that the most important NBO interactions are those between the carbonyl groups and the adjacent C−O and C−C bonds.
URI: http://hdl.handle.net/10316/10654
ISSN: 1089-5639
DOI: 10.1021/jp805603b
Rights: openAccess
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais

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