A Matrix Isolation Spectroscopic and Quantum Chemical Study of Fumaric and Male...

• Autor(es): Maçôas, Ermelinda M. S. ; Fausto, Rui ; Lundell, Jan ; Pettersson, Mika ; Khriachtchev, Leonid ; Räsänen, Markku
• Data: 2001
• Identificador Persistente: http://hdl.handle.net/10316/10528
• Origem: Estudo Geral - Universidade de Coimbra
• Tipo de Documento: Artigo
• Idioma: Inglês

Descrição

Relative energies and vibrational spectra of buthenedioic acid [(E)- and (Z)-HOOC−CHCH−COOH; fumaric and maleic acids] were calculated using Hartree−Fock (HF), Møller−Plesset to 2nd order (MP2), and B3LYP Density Functional Theory (DFT) levels of approximation. Computationally the lowest energy conformer of maleic acid has a nearly planar structure with an OH···OC intramolecular hydrogen bond closing a seven member ring. Second conformer of maleic acid adopts a cis arrangement around the C−O bonds and exhibits the two carbonyl bonds in a nearly orthogonal arrangement with one carboxylic group in the plane containing the carbon atoms. Fumaric acid has three planar conformers with relative energies within 5 kJ mol-1. These conformers exhibit a cis arrangement around the C−O bond and differ by the relative conformation of their OC−CC axes. The infrared spectra of the studied compounds isolated in a solid argon matrix feature the most stable conformers. Narrowband tunable irradiation in the near-infrared region (6901 cm-1) was found to promote a conversion of the second most stable conformer of maleic acid into the most stable conformer. http://dx.doi.org/10.1021/jp003802p