Aromatic and Acetylenic C-H or C-D Stretching Bands Anharmonicity Detection of Phenylacetylene by UV Laser-Induced Vibrational Emission.

The anharmonic infrared (IR) emission spectra of phenylacetylene C 6 H 5 CCH and an isotopologue C 6 H 5 CCD induced by 193 nm UV excitation have been investigated in the gas phase. The study has been operated with a homemade IR spectrometer enabling to record time- and wavelength-resolved spectra between 2.5 and 4.5 μm, emitted all along the collisional cooling. The analysis is supported by a kinetic Monte Carlo simulation in the vibrational harmonic approximation. For both species, the anharmonic shifts of the acetylenic C-H or C-D stretching modes and the aromatic C-H stretching modes are studied for band positions and bandwidths in terms of the internal energy. For C 6 H 5 CCD, the internal energy dependence of the emission intensity band ratio is investigated and rationalized. This work demonstrates the potential of time-resolved IR emission spectroscopy to explore anharmonicity of astrophysically relevant molecules.