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The C-H (Delta upsilon = 6) absorption spectrum of methane has been obtained in liquid nitrogen and argon solutions using thermal lens spectroscopy. Mathematical models for continuous and periodic excitation were used to describe the concentration dependence of thermal lens intensities. Better fitting of the experimental results was accomplished by taking into account the periodic nature of the excitation. Comparison of thermal lens intensities in nitrogen and argon allowed calculation of relative enhancement factors. In dilute solutions, the intensity in liquid nitrogen was 1.39 +/- 0.08 times higher than that in argon. The literature estimation of this ratio is 1.49 +/- 0.61. In contrast to the estimated value, our result confidently shows actual variation in enhancement factors. This article not only shows the applicability of thermal lensing to cryosamples but also demonstrates that accurate measurements at low temperature are possible.

This article presents a collection of vibrational overtone spectra of hydrocarbons in cryogenic solutions. Vibrational overtone spectra of ethane and propane dissolved in liquid argon and n-butane and isobutane dissolved in liquid krypton were recorded between 5000 and 14,000 cm(-1). Spectral regions for the first four overtones were measured using a Fourier transform spectrophotometer. The fifth overtone (Deltaupsilon = 6) spectra were recorded with a double beam (pump-probe) thermal lens technique using concentrations as low as 10-3 mole fraction. We obtained the C-H (Deltaupsilon = 6) spectra of (a) liquid ethane at 100 K and ethane in solutions in liquid Ar at 92 K and liquid N2 at 85 K, (b) liquid propane at 148 K and propane in liquid Ar at 93 K, (c) n-butane in liquid Kr at 129 K, (d) n-pentane in liquid Xe at 160 K, and (e) isobutane liquid at 135 K and isobutane in liquid Kr at 130 K. Local-mode parameters were calculated for primary, secondary, and tertiary C-H oscillators in solution and compared with gas-phase local-mode parameters. The peak frequency shift (Deltaomega) from gas phase to solution is explained by the change in harmonic frequency and anharmonicity in solution with respect to the gas-phase values. The bandwidth (Deltaomega1/2) of the (Deltaupsilon = 6) C-H absorption bands of ethane in solution can be explained in terms of collisions with the solvent molecules.

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