Line Mixing and Broadening in the Raman Q Branch of HD at 304.6 K.

The Q-branch lines of pure HD were measured at densities ranging from 1 to 7 Amagat at 304.6 K. Each profile was fitted to the well-known Rosenkranz expression to extract the size of the asymmetry due to line mixing as well as to the linewidth. Line mixing and broadening coefficients were obtained by fitting the asymmetries and widths to a straight line as a function of gas density. Apart from a single existing measurement for the Q(0) line, our mixing coefficients are the first direct measurements of the asymmetry due to line mixing in HD. Our broadening coefficients are consistent with the best earlier measurements but are an order of magnitude more precise. Agreement is found with some existing semiclassical calculations of broadening. We have fitted our HD broadening coefficients to a variety of empirical energy gap laws. Our conclusions are that none of the exponential gap law (EGL), the modified exponential gap (MEG) law, and the statistical power gap (SPG) law successfully models our broadening coefficients. We present a modified version of the EGL and the MEG laws, which are successful in reproducing the experimental results. Using the fitted parameters of the new gap law, we have calculated the relaxation matrix of HD at room temperature. With this relaxation matrix, we have simulated the Q-branch spectrum at a number of densities between 49.1 and 490 Amagat and compared the results with previous high-density measurements. At all densities and frequencies, the simulated spectral intensity was found to agree with the measured strength within about 5% of the peak of the spectrum. In addition, the comparison provides evidence of a nonlinear vibrational dephasing shift in HD. Copyright 1998 Academic Press.