Maximum entropy distributions of wave functions at thermal equilibrium

Jacob T Willson1, Henrik J Heelweg1, Adam P Willard1

  • 1Massachusetts Institute of Technology, Department of Chemistry, Cambridge, Massachusetts 02139, USA.

Physical Review. E
|August 22, 2026
PubMed

Related Concept Videos

Absolute Entropies and the Third Law of Thermodynamics01:23

Absolute Entropies and the Third Law of Thermodynamics

Ludwig Edward Boltzmann developed a definition for entropy, which stated that absolute entropy is proportional to the natural logarithm of the number of possible combinations of particles. Entropy stands alone among state functions as the only one whose absolute values can be determined.Consider a gas sample confined to a container. As the container expands, the energy levels of gas molecules become more closely spaced. This increases the number of available energy states, thereby increasing...
Third Law of Thermodynamics02:38

Third Law of Thermodynamics

A pure, perfectly crystalline solid possessing no kinetic energy (that is, at a temperature of absolute zero, 0 K) may be described by a single microstate, as its purity, perfect crystallinity,and complete lack of motion means there is but one possible location for each identical atom or molecule comprising the crystal (W = 1). According to the Boltzmann equation, the entropy of this system is zero.
Entropy02:39

Entropy

Salt particles that have dissolved in water never spontaneously come back together in solution to reform solid particles. Moreover, a gas that has expanded in a vacuum remains dispersed and never spontaneously reassembles. The unidirectional nature of these phenomena is the result of a thermodynamic state function called entropy (S). Entropy is the measure of the extent to which the energy is dispersed throughout a system, or in other words, it is proportional to the degree of disorder of a...
Entropy01:18

Entropy

The first law of thermodynamics is quantitatively formulated via an equation relating the internal energy of a system, the heat exchanged by it, and the work done on it. A quantitative formulation of the second law of thermodynamics leads to defining a state function, the entropy.
When an ideal gas expands isothermally, the disorder in the gas increases. From the molecular perspective, the gas molecules have more volume to move around in.
Consider an infinitesimal step in the expansion, which...
Atomic Nuclei: Nuclear Spin State Population Distribution01:14

Atomic Nuclei: Nuclear Spin State Population Distribution

Near absolute zero temperatures, in the presence of a magnetic field, the majority of nuclei prefer the lower energy spin-up state to the higher energy spin-down state. As temperatures increase, the energy from thermal collisions distributes the spins more equally between the two states. The Boltzmann distribution equation gives the ratio of the number of spins predicted in the spin −½ (N−) and spin +½ (N+) states.
Entropy and the Second Law of Thermodynamics01:20

Entropy and the Second Law of Thermodynamics

The second law of thermodynamics can be stated quantitatively using the concept of entropy. Entropy is the measure of disorder of the system.
The relation  between entropy and disorder can be illustrated with the example of the phase change of ice to water. In ice, the molecules are located at specific sites giving a solid state, whereas, in a liquid form, these molecules are much freer to move. The molecular arrangement has therefore become more randomized. Although the change in average...