Narrowband NIR-Induced In Situ Generation of the High-Energy Trans Conformer of Trichloroacetic Acid Isolated in Solid Nitrogen and its Spontaneous Decay by Tunneling to the Low-Energy Cis Conformer

• Autor(a) principal: Apóstolo, R. F. G.
• Data de Publicação: 2015
• Outros Autores: Bento, R. R. F., Fausto, Rui
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
• Texto Completo: http://hdl.handle.net/10316/109090; https://doi.org/10.5562/cca2704
• topic: trichloroacetic acid; NIR-induced in situ generation of the higher energy trans-TCA conformer; spontaneous decay by tunneling; matrix-isolation infrared spectroscopy; quantum chemical calculations

The monomeric form of trichloroacetic acid (CCl3COOH; TCA) was isolated in a cryogenic nitrogen matrix (15 K) and the higher energy trans conformer (O=C–O–H dihedral: 180°) was generated in situ by narrowband near-infrared selective excitation the 1st OH stretching overtone of the low-energy cis conformer (O=C–O–H dihedral: 0°). The spontaneous decay, by tunneling, of the generated high-energy conformer into the cis form was then evaluated and compared with those observed previously for the trans conformers of acetic and formic acids in identical experimental conditions. The much faster decay of the high-energy conformer of TCA compared to both formic and acetic acids (by ~35 and ca. 25 times, respectively) was found to correlate well with the lower energy barrier for the trans → cis isomerization in the studied compound. The experimental studies received support from quantum chemistry calculations undertaken at the DFT(B3LYP)/cc-pVDZ level of approximation, which allowed a detailed characterization of the potential energy surface of the molecule and the detailed assignment of the infrared spectra of the two conformers.