Matrix Isolation Study of Fumaric and Maleic Acids in Solid Nitrogen

[Image: see text] Fumaric and maleic acids ((E)- and (Z)-HOOC–CH=CH–COOH, FA and MA) were studied experimentally by infrared spectroscopy in nitrogen matrixes and theoretically by quantum chemical calculations. The calculations, carried out at the DFT(B3LYP) and MP2 levels of theory, predicted the existence of at least 5 conformers of maleic acid and 10 conformers of fumaric acid. After the deposition of the matrixes, two conformers of maleic acid (I and II) and three conformers (I–III) of fumaric acid were observed and characterized vibrationally. Selective narrowband near-infrared (NIR) excitation of the first OH stretching overtones of the different conformers of maleic and fumaric acids initially present in the matrixes allowed the generation of higher-energy forms, never before observed experimentally. In the case of maleic acid, conformers I (a cis–trans form, where cis and trans designate the conformation of the carboxylic groups of the molecule) and II (cis–cis) were found to generate the novel conformers VI (trans–trans) and VII (cis–trans), respectively. The conversion of conformer II into the most stable conformer I was also observed. For fumaric acid, the cis–cis conformers I–III were found to give rise to the new cis–trans conformers IV–VII, respectively. The tunneling decay of the new conformers produced upon NIR excitation of the lowest-energy conformers initially trapped in the matrixes was observed, and their lifetimes in solid N(2) were determined. The increased stability of all of the observed high-energy conformers of the studied acids in the N(2) matrix, compared to the argon matrix, where they could not be observed experimentally, demonstrates the stabilizing effect of the interaction between the OH groups of the acids with the matrix N(2) molecules, in line with previous observations for other carboxylic acids. In addition, the photochemistry of matrix-isolated maleic and fumaric acids upon broad-band UV irradiation (λ > 235 nm) was also investigated. UV-induced isomerization of both acids around the C=C double bond was observed, together with their decarboxylation to acrylic acid.