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=CO (2.075 Å) and a HC(OH)O⋅⋅⋅CO2 (2.877 Å) interactions. The ab initio intermolecular binding energy, obtained at the counterpoise corrected MP2/aug-cc-pVTZ level of calculation, is De =17 kJ mol(-1) .
Vigorito, A., Gou, Q., Calabrese, C., Melandri, S., Maris, A., Caminati, W. (2015). How CO<inf>2</inf> Interacts with Carboxylic Acids: A Rotational Study of Formic Acid-CO<inf>2</inf>. CHEMPHYSCHEM, 16(14), 2961-2967 [10.1002/cphc.201500531].
How CO2 Interacts with Carboxylic Acids: A Rotational Study of Formic Acid-CO2
VIGORITO, ANNALISA;GOU, QIAN;CALABRESE, CAMILLA;MELANDRI, SONIA;MARIS, ASSIMO;CAMINATI, WALTHER
2015
Abstract
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=CO (2.075 Å) and a HC(OH)O⋅⋅⋅CO2 (2.877 Å) interactions. The ab initio intermolecular binding energy, obtained at the counterpoise corrected MP2/aug-cc-pVTZ level of calculation, is De =17 kJ mol(-1) .I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
