Pressure shifts in the vibrational Raman spectra of hydrogen and deuterium, 315–85 K

Abstract

The Raman frequencies of the Q(J) lines of the fundamental Raman bands of compressed H2 and D, were measured with a standard deviation of ±0.02 cm−1 at gas densities from 10 to 100 amagat at several temperatures in the range 315 to 85 K. The frequency shifts are negative and linear in the gas density; they range up to −1.2 cm−1 for H2 and −0.7 cm−1 for D2. The linear coefficient for the Q(J) line has the form, ai + ac(nJ/n), where nJ/n is the fractional population of the rotational level, J, and ai and ac are constants independent of J. The constant ai is strongly temperature-dependent and is interpreted as the vibrational shift due to isotropic dispersion and overlap forces. On the other hand, ac is practically temperature-independent and is believed to arise from vibrational coupling through dispersion forces.