Please use this identifier to cite or link to this item:
https://hdl.handle.net/10316/10675
DC Field | Value | Language |
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dc.contributor.author | Maçôas, Ermelinda M. S. | - |
dc.contributor.author | Fausto, Rui | - |
dc.contributor.author | Lundell, Jan | - |
dc.contributor.author | Pettersson, Mika | - |
dc.contributor.author | Khriachtchev, Leonid | - |
dc.contributor.author | Räsänen, Markku | - |
dc.date.accessioned | 2009-07-14T08:22:02Z | - |
dc.date.available | 2009-07-14T08:22:02Z | - |
dc.date.issued | 2000-12-21 | - |
dc.identifier.citation | The Journal of Physical Chemistry A. 104:50 (2000) 11725-11732 | en_US |
dc.identifier.issn | 1089-5639 | - |
dc.identifier.uri | https://hdl.handle.net/10316/10675 | - |
dc.description.abstract | Relative energies and vibrational spectra of the conformational states of a malonic acid monomer (HOOCCH2COOH) were calculated using various levels of approximation [Hartree−Fock (HF), Møller−Plesset to second order (MP2), and B3LYP density functional theory (DFT)]. The calculations predict the existence of six different conformers according to skeletal C−C bond and O−H bond rotation. Three conformers are found with energies close enough to enable their spectroscopic observation. The lowest-energy conformer (I) shows a nearly planar structure with an OH···OC intramolecular hydrogen bond closing a six-member ring. The second- and third-lower energy conformers (II and III) differ from the conformational ground state by less than 5 kJ mol-1. Conformers II and III adopt a cis arrangement around the C−O bonds: conformer II exhibits the two carbonyl bonds in a nearly orthogonal arrangement, with one carboxylic group in the plane containing the carbon atoms, whereas in conformer III (C2 symmetry), the carbonyl bonds make a dihedral angle of ca. 120°, and both carboxylic groups are placed out of the plane containing the skeletal carbons. Their relative energy is predicted by the highest-level calculations to be ca. 1 kJ mol-1. The theoretical predictions agree with the analysis of the infrared spectra of monomeric malonic acid isolated in a solid argon matrix, where the presence of the three above-mentioned conformers was unequivocally identified. Narrowband tunable irradiation in the near-infrared region was found to promote efficiently the interconversion between the experimentally observed conformers. | en_US |
dc.language.iso | eng | en_US |
dc.publisher | American Chemical Society | en_US |
dc.rights | openAccess | eng |
dc.title | Conformational Analysis and Near-Infrared-Induced Rotamerization of Malonic Acid in an Argon Matrix | en_US |
dc.type | article | en_US |
dc.identifier.doi | 10.1021/jp002853j | - |
uc.controloAutoridade | Sim | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.openairetype | article | - |
item.cerifentitytype | Publications | - |
item.grantfulltext | open | - |
item.fulltext | Com Texto completo | - |
item.languageiso639-1 | en | - |
crisitem.author.researchunit | CQC - Coimbra Chemistry Centre | - |
crisitem.author.parentresearchunit | Faculty of Sciences and Technology | - |
crisitem.author.orcid | 0000-0002-8264-6854 | - |
Appears in Collections: | FCTUC Química - Artigos em Revistas Internacionais |
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File | Description | Size | Format | |
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Conformational Analysis and Near-Infrared-Induced Rotamerization of Malonic Acid.pdf | 101.76 kB | Adobe PDF | View/Open |
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