Helmholtz energy function

Hermann Ludwig Ferdinand von Helmholtz Definition of A (for arbeit):

$\left.A\right.=U-TS$

where U is the internal energy, T is the temperature and S is the entropy. (TS) is a conjugate pair. The differential of this function is

$\left.dA\right.=dU-TdS-SdT$

From the second law of thermodynamics one obtains

$\left.dA\right.=TdS-pdV-TdS-SdT$

thus one arrives at

$\left.dA\right.=-pdV-SdT$.

For A(T,V) one has the following total differential

$dA=\left({\frac {\partial A}{\partial T}}\right)_{V}dT+\left({\frac {\partial A}{\partial V}}\right)_{T}dV$

The following equation provides a link between classical thermodynamics and statistical mechanics:

$\left.A\right.=-k_{B}T\ln Q_{NVT}$

where $k_{B}$ is the Boltzmann constant, T is the temperature, and $Q_{NVT}$ is the canonical ensemble partition function.

See also

• Canonical ensemble
• Grand canonical ensemble

References

1. Enrique de Miguel, Ramona G. Marguta and Elvira M. del Río "System-size dependence of the free energy of crystalline solids", Journal of Chemical Physics 127 154512 (2007)