Doppler-limited spectroscopy at cryogenic temperatures: Application of collisional cooling

Abstract

A coolable gas cell for the measurement of mid-infrared spectra of gases at cryogenic temperatures as low as 77 K is described. The design of the cell allows it to be operated in collisional cooling (or diffusive trapping) mode to generate significant nonequilibrium pressures of monomer vapor for gases which would normally have vanishingly small vapor pressure at low temperatures. Fourier transform infrared spectra of carbon dioxide (CO2), nitrogen dioxide (NO2), and methyl silane (CH3SiH3) vapors cooled by collisions with helium gas at 77 K are reported. Sufficiently high concentrations of monomer gas may be produced at low total pressure conditions (<10 h Pa) to allow spectra to be recorded at the Doppler resolution limit. The resulting spectroscopic simplification indicates that efficient collisional cooling of the vibrational, as well as rotational, degrees of freedom occurs.