Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/10654
DC FieldValueLanguage
dc.contributor.authorJarmelo, S.-
dc.contributor.authorReva, I. D.-
dc.contributor.authorLapinski, L.-
dc.contributor.authorNowak, M. J.-
dc.contributor.authorFausto, R.-
dc.date.accessioned2009-07-13T09:38:15Z-
dc.date.available2009-07-13T09:38:15Z-
dc.date.issued2008-11-06-
dc.identifier.citationThe Journal of Physical Chemistry A. 112:44 (2008) 11178-11189en_US
dc.identifier.issn1089-5639-
dc.identifier.urihttp://hdl.handle.net/10316/10654-
dc.description.abstractThe 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.en_US
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsopenAccesseng
dc.titleMatrix-Isolated Diglycolic Anhydride: Vibrational Spectra and Photochemical Reactivityen_US
dc.typearticleen_US
dc.identifier.doi10.1021/jp805603b-
uc.controloAutoridadeSim-
item.fulltextCom Texto completo-
item.grantfulltextopen-
item.languageiso639-1en-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.orcid0000-0001-5771-458X-
crisitem.author.orcid0000-0001-5983-7743-
crisitem.author.orcid0000-0003-2896-4007-
crisitem.author.orcid0000-0002-8264-6854-
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais
Files in This Item:
File Description SizeFormat
Matrix-Isolated Diglycolic Anhydride.pdf621.92 kBAdobe PDFView/Open
Show simple item record

SCOPUSTM   
Citations

8
checked on May 29, 2020

WEB OF SCIENCETM
Citations 5

10
checked on Aug 2, 2022

Page view(s) 50

411
checked on Sep 27, 2022

Download(s)

238
checked on Sep 27, 2022

Google ScholarTM

Check

Altmetric

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.