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How CO 2 Interacts with Carboxylic Acids: A Rotational Study of Formic Acid–CO 2
Author(s) -
Vigorito Annalisa,
Gou Qian,
Calabrese Camilla,
Melandri Sonia,
Maris Assimo,
Caminati Walther
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500531
Subject(s) - isotopologue , chemistry , quadrupole , rotational spectroscopy , ab initio quantum chemistry methods , rotational transition , rotational energy , analytical chemistry (journal) , intermolecular force , ab initio , cyclohexane , hyperfine structure , atomic physics , molecule , angular momentum , physics , organic chemistry , quantum mechanics , chromatography
The rotational spectra of the 1:1 formic acid–carbon dioxide molecular complex and of its monodeuterated isotopologues are analysed in the 6.5–18.5 and 59.6–74.4 GHz frequency ranges using a pulsed jet Fourier transform microwave spectrometer and a free‐jet absorption millimetre wave spectrometer, respectively. Precise values of the rotational and quartic centrifugal distortion constants are obtained from the measured frequencies, and quadrupole coupling constants are determined from the deuterium hyperfine splittings. Structural parameters are estimated from the moments of inertia and their differences among isotopologues: the complex has a planar structure with the two subunits held together by a HC(O)OH⋅⋅⋅O=C O (2.075 Å) and a HC(OH)O⋅⋅⋅CO 2 (2.877 Å) interactions. The ab initio intermolecular binding energy, obtained at the counterpoise corrected MP2/aug‐cc‐pVTZ level of calculation, is D e =17 kJ mol −1 .