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Journal of Chemical Education

Negative Absolute Temperatures, a Novelty

Jaime Wisniak

Published Apr 1, 2000• 6 citations
Publisher

Abstract

The concept of absolute temperature is developed on the basis of the second law. It is shown that although, in general, the absolute temperature can take only positive values, it can achieve negative values for particular cases where only a finite number of energy levels are available.
DOI
10.1021/ed077p518

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Inverted quantum states provide a challenge to classical thermodynamics, since they appear to contradict the classical formulation of the second law of thermodynamics. Ramsey interpreted these states as stable equilibrium states of negative thermodynamic temperature, and added a provision to allow these states to the Kelvin-Planck statement of the second law [N. F. Ramsey, Phys. Rev. 103, 20 (1956)PHRVAO0031-899X10.1103/PhysRev.103.20]. Since then, Ramsey's interpretation has prevailed in the literature. Here, we present an alternative option to accommodate inverted states within thermodynamics, which strictly enforces the original Kelvin-Planck statement of the second law, and reconciles inverted states and the second law by interpreting the former as unstable states, for which no temperature-positive or negative-can be defined. Specifically, we recognize inverted quantum states as temperature-unstable states, for which all processes are in agreement with the original Kelvin-Planck statement of the second law, and positive thermodynamic temperatures in stable equilibrium states. These temperature-unstable states can only be created by work done to the system, which is stored as energy in the unstable states, and can be released as work again, just as in a battery or a spring.
The second and third laws of thermodynamics can be used to establish a fundamental bound for the maximum possible cooling rate in approaching the absolute zero of temperature. In modeling the behavior of the molecular refrigerators geared toward attaining ultralow temperatures, only quantum mechanical, as opposed to classical physics, models can be admissible. As a simple model, we analyze a three-level quantum refrigerator, and in particular its irreversible thermodynamic performance as absolute zero is approached.
Absolute temperature is usually bound to be positive. Under special conditions, however, negative temperatures-in which high-energy states are more occupied than low-energy states-are also possible. Such states have been demonstrated in localized systems with finite, discrete spectra. Here, we prepared a negative temperature state for motional degrees of freedom. By tailoring the Bose-Hubbard Hamiltonian, we created an attractively interacting ensemble of ultracold bosons at negative temperature that is stable against collapse for arbitrary atom numbers. The quasimomentum distribution develops sharp peaks at the upper band edge, revealing thermal equilibrium and bosonic coherence over several lattice sites. Negative temperatures imply negative pressures and open up new parameter regimes for cold atoms, enabling fundamentally new many-body states.