In Raman spectroscopy you have to deal with Rayleigh scattering and (Anti-)Stokes scattering. The intensity of Rayleigh scattering is about 5 magnitudes lower than the laser's excitation intensity, then the Stokes intensity is another 3 magnitudes lower and Anti-Stokes intensity another 3 magnitudes.
I understand that according to the Boltzmann distribution systems have lower probability of being in higher energy states. Since Anti-Stokes scattering requires a molecule to be in a higher energy state to begin with, it seems logical to me that this type of scattering is less likely than Rayleigh or Stokes scattering.
However Rayleigh and Stokes scattering both can start from the same energy state. Does the Boltzmann distribution also mean it is less likely for a molecule to end up in a higher state than it originally started? In other words: Does a molecule tend to try to emit as much energy as possible?