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Infrared Spectra of Cyanoacetaldehyde (NCCH 2 CHO): A Potential Prebiotic Compound of Astrochemical Interest
Author(s) -
Benidar Abdessamad,
Georges Robert,
Guillemin JeanClaude,
Mó Otilia,
Yáñez Manuel
Publication year - 2013
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.201300354
Subject(s) - conformational isomerism , dihedral angle , chemistry , alkane stereochemistry , anharmonicity , infrared , ab initio , density functional theory , infrared spectroscopy , crystallography , potential energy surface , molecular physics , computational chemistry , physics , molecule , crystal structure , hydrogen bond , optics , organic chemistry , quantum mechanics
Abstract Cyanoacetaldehyde (NCCH 2 CHO) and its isomer, cyanovinylalcohol (NCCHCHOH), as possible components of the interstellar medium, comets, or planetary atmospheres, exist in equilibrium in the gas phase, although the latter compound is very much in the minority (2 %). The recording and analysis of the gas‐phase infrared spectrum of the former compound within the 4000–500 cm −1 spectroscopic range and the potential presence of the latter isomer, which could be vital for their detection in these media, are reported. CCSD(T) and G4 high‐level ab initio methods, as well as density functional theory calculations, predict the existence of two stable rotamers of cyanoacetaldehyde. The global minimum has a structure with an unusual O‐C‐C‐C dihedral angle (150°) that falls between the antiperiplanar (180°) and anticlinal forms (120°). The second rotamer, which is about 4.0 kJ mol −1 less stable in terms of free energy, has a planar structure that corresponds to the synperiplanar form (O‐C‐C‐C dihedral angle: 0°). The absorption vibrational bands of the two aldehyde rotamers that are present in the mixture lead to a spectrum with a very complex structure in the region of deformation movements, in which several low‐intensity bands overlap. A complete and unambiguous assignment of the experimental spectrum has been achieved by using the calculated harmonic and anharmonic vibrational frequencies.