Thermodynamic integration with harmonic reference
The Helmholtz free energy ([math]\displaystyle{ A }[/math]) of a fully interacting system (1) can be expressed in terms of that of harmonic system (0) as follows
- [math]\displaystyle{ A_{1} = A_{0} + \Delta A_{0\rightarrow 1} }[/math]
where [math]\displaystyle{ \Delta A_{0\rightarrow 1} }[/math] is anharmonic free energy. The latter term can be determined by means of thermodynamic integration
- [math]\displaystyle{ \Delta A_{0\rightarrow 1} = \int_0^1 d\lambda \langle V_1 -V_0 \rangle_\lambda }[/math]
with [math]\displaystyle{ V_i }[/math] being the potential energy of system [math]\displaystyle{ i }[/math], [math]\displaystyle{ \lambda }[/math] is a coupling constant and