High resolution TDL spectroscopy of the Ar-CH4 complex.

The spectrum of the weakly bound complex Ar-CH4 in the 7 microm region was discovered, analysed, and compared with a spectrum, predicted from ab initio calculations. The measurements were made by probing a supersonic gas expansion with a tunable diode laser (TDL). Several bands of Ar-CH4 associated with different ro-vibrational transitions of the v4 vibration of CH4 were recorded and analysed in a spectral region from 1295 to 1330 cm(-1). In particular the following transitions were studied: j = 1 <-- 0 (at 1311 cm(-1)) reported in Pak et al. [Z. Naturforsch. 53 (1998) 725], j = 0 <-- 1 (at 1301 cm(-1)), j = 2 <-- 1 (at 1316 cm(-1)), and j = 3 <-- 2 transitions (at 1322 cm(-1)). Here, j denotes the angular momentum of the methane unit inside the complex. Analysis of the recently recorded j = 1 <-- 1 transitions at about 1306 cm(-1) in the region of methane Q(1) is in progress. The experimental results are compared with ab initio calculations. The close agreement between observed and ab initio spectra is convincingly demonstrated with respect to the gross spectral features, including many details of the spectra.

Vibrational predissociation dynamics of methane-Ar: an ab initio approach.

We calculated the cross sections for vibrational predissociation of methane-Ar induced by excitation of the methane nu 3 mode with the aid of an ab initio CH4-Ar potential depending explicitly on the nu 3 and nu 1 normal coordinates of the CH4 monomer. We found that dissociation into CH4 fragments excited in the nu 1 mode, a V-->V' process with very low kinetic energy release, strongly dominates over direct dissociation into Ar and ground state CH4, and is responsible for the line broadening observed experimentally. The (observed and calculated) strong variation of the line widths for the Van der Waals levels excited in combination with the nu 3 mode (giving states of A, F and E symmetry) is related to the opening up of appropriate nu 1 dissociation channels and the occurrence of rotational resonances in the nu 1 continuum in the energy range of the quasi-bound nu 3 levels.