US EPA

3858433 

Journal Article 

Rotational spectroscopic and theoretical study of the perfluorobutyric acid center dot center dot center dot formic acid complex 

Thomas, J; Carrillo, MJ; Serrato, A III; Lin, Wei; Jaeger, W; Xu, Y 

2017 

Yes 

Journal of Molecular Spectroscopy
ISSN: 0022-2852
EISSN: 1096-083X 

335 

88-92 

10.1016/j.jms.2017.03.015 

WOS:000400716000017 

Perfluorinated carboxylic acids are a special class of compounds with considerable industrial applications. In this study, we applied chirped pulse and cavity-based Fourier transform microwave spectroscopy to investigate the structural and possible tunneling properties of the perfluorobutyric acid center dot center dot center dot formic acid complex, together with high level ab initio calculations. Only one clearly dominant conformer, featuring an eight-membered double hydrogen-bonded ring, was predicted for the hetero acid dimer and detected experimentally. The rotational constants calculated at the B3LYP-D3BJ/6-311++G(2d, p) level are in excellent agreement with the experimental ones, better than those from MP2 calculations. No tunneling splittings were detected in the experimental spectra. Detailed analyses of the non-covalent intermolecular interactions in the hetero acid dimer provide an explanation for the absence of double proton transfer, and also identify the presence of F center dot center dot center dot F attractive interactions. (C) 2017 Elsevier Inc. All rights reserved. 

Carboxylic acid dimer; Double proton transfer; F center dot center dot center dot F attractive interaction; Perfluorinated acids; Chirped pulse and cavity FTMW spectroscopy; Hydrogen bonding