Mode-coupling theory of the fifth-order Raman spectrum of an atomic liquid.

A fully microscopic molecular hydrodynamic theory for the two-dimensional (fifth-order) Raman spectrum of an atomic liquid (Xe) is presented. The spectrum is obtained from a simple mode-coupling theory by projecting the dynamics onto bilinear pairs of fluctuating density variables. Good agreement is obtained in comparison with recently reported molecular dynamics simulation results. The microscopic theory provides an understanding of the timescales and molecular motions that govern the two-dimensional signal. Predictions are made for the behavior of the spectrum as a function of temperature and density. The theory shows that novel signatures in the two-dimensional Raman spectrum of supercritical and supercooled liquids are expected.