Helmholtz free energy is a thermodynamic potential that measures the amount of useful work obtainable from a closed system at constant temperature and volume. It is defined as the internal energy of the system minus the product of its temperature and entropy, represented mathematically as $$A = U - TS$$. This concept plays a crucial role in statistical mechanics and ensemble theory, where it helps to connect macroscopic thermodynamic properties with microscopic states of a system, thereby providing insights into the system's behavior under various conditions.
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