Cédric Bray

Full Conformational Landscape of 3-Methoxyphenol Revealed by Room Temperature mm-wave Rotational Spectroscopy Supported by Quantum Chemical Calculations

Room temperature millimeter-wave rotational spectroscopy supported by high level of theory calculations have been employed to fully characterise the conformational landscape of 3-Methoxyphenol, a semi-volatile polar oxygenated aromatic compound precursor of secondary organic aerosols in the atmosphere arising from biomass combustion. While previous rotationally-resolved spectroscopic studies in the microwave and in the UV domains failed to observe the complete conformational landscape, the 70-330 GHz rotational spectrum measured in this study reveals the ground state rotational signatures of the four stable conformations theoretically predicted. Moreover, rotational transitions in the lowest energy vibrationally excited states were assigned for two conformers. While the inertial defect of methoxyphenol does not significantly change between conformers and isomers, the excitation of the methoxy out-of-plane bending is the main contribution to the non-planarity of the molecule.

LINE POSITIONS OF CENTRIFUGAL DISTORSION INDUCED ROTATIONAL TRANSITIONS OF METHANE MEASURED UP TO 2.6 THZ AT SUB-MHZ ACCURACY WITH A CW-THZ PHOTOMIXING SPECTROMETER

Several Doppler limited rotational transitions of methane induced by centrifugal distortion have been measured with an unprecedented frequency accuracy using the THz photomixing synthesizer based on a frequency comb. Compared to previous synchrotron based FT-Far-IR measurements of Boudon et al.a, the accuracy of the line frequency measurements is improved by one order of magnitude, this yields a corresponding increase of two orders of magnitude to the weighting of these transitions in the global fit. The rotational transitions in the ν4 ← ν4 hot band are measured for the first time by the broad spectral coverage of the photomixing CW-THz spectrometer providing access up to R(5) transitions at 2.6 THz. The new global fit including the present lines has been used to update the methane line list of the HITRAN database. Some small, but significant variations of the parameter values are observed and are accompanied by a reduction of the 1-σ uncertainties on the rotational (B0) and centrifugal distortion (D0) constants.