Time autocorrelations of intermolecular interactions and impact broadening of vibration-rotation lines. I. Rotational Raman effect in gaseous hydrogen and deuterium

Abstract

The second-order perturbation expressions for the Raman vibration-rotation half-widths are derived which can be applied to any dense medium. These are used to deduce the Fourier transform spectra of the anisotropic H 2-H 2 interaction potential from the rotational broadening data on gaseous hydrogen and deuterium. Reliability and accuracy of the solution of this partial inverse problem are obtained by the linear regression analysis. The computer simulations undertaken for room temperature hydrogen reveal the predominant role of the doubly anisotropic quadrupolar forces in the rotational broadening. The computed spectra are shown to be sensitive to the details of the potential surface.