Temperature Integration: An efficient procedure for calculation of free energy differences

We propose a method, Temperature Integration, which allows an efficient calculation of free energy differences between two systems of interest, with the same degrees of freedom, which may have rough energy landscapes. The method is based on calculating, for each single system, the difference between the values of In Z at two temperatures, using a Parallel Tempering procedure. If our two systems of interest have the same phase space volume, they have the same values of In Z at high-T, and we can obtain the free energy difference between them, using the two single-system calculations described above. If the phase space volume of a system is known, our method can be used to calculate its absolute (versus relative) free energy as well. We apply our method and demonstrate its efficiency on a "toy model" of hard rods on a 1-dimensional ring. (C) 2013 Elsevier B.V. All rights reserved.