Thermodynamic integration with harmonic reference: Difference between revisions

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:<math>
:<math>
A_{1} = A_{0} + \Delta A_{0\rightarrow 1}
A_{1} = A_{0} + \Delta A_{0\rightarrow 1}
</math>  
</math>  
where <math>\Delta A_{0\rightarrow 1}</math> is anharmonic free energy. The latter term
where <math>\Delta A_{0\rightarrow 1}</math> is anharmonic free energy. The latter term can be determined by means of thermodynamic integration
:<math>
\Delta A_{0\rightarrow 1} = \int_0^1 d\lambda \langle V_1 -V_0  \rangle_\lambda
</math>
with <math>V_i</math> being the potential energy of system <math>i</math>, <math>\lambda</math> is a coupling constant and

Revision as of 07:35, 1 November 2023

The Helmholtz free energy () of a fully interacting system (1) can be expressed in terms of that of harmonic system (0) as follows

where is anharmonic free energy. The latter term can be determined by means of thermodynamic integration

with being the potential energy of system , is a coupling constant and