Helium induced pressure broadening and shifting of HCN hyperfine transitions between 1.3 and 20 K.

We have measured the helium induced pressure broadening and shifting of the distinct hyperfine components of the j=1←0 and j=2←1 transitions of HC¹⁴N at temperatures between 1.3 and 20 K. The HCN molecules were cooled to these temperatures using the collisional cooling technique. As a test of this cooling technique we measured the Doppler contribution to the spectral lines, and these measurements confirm that the molecules are at the same temperature as the walls of the spectroscopic cell. We observed that the hyperfine components of the 2←1 transition have distinct broadening coefficients that differ from one another by as much as 5%. The measured differences are in reasonable agreement with theoretical predictions. We have also performed molecular scattering calculations on three He–HCN potential energy surfaces in order to compare our results with theoretical expectations. At the lowest temperatures these calculations predict broadening coefficients that are considerably larger than the measured coefficients. We have previously found a similar discrepancy for two other molecules at these low temperatures, and we discuss possible experimental and theoretical origins for this persistent discrepancy. [ABSTRACT FROM AUTHOR]