Certain systems can achieve negative thermodynamic temperature; that is, their temperature can be expressed as a negative quantity on the Kelvin or Rankine scales. This should be distinguished from temperatures expressed as negative numbers on non-thermodynamic Celsius or Fahrenheit scales, which are nevertheless higher than absolute zero.
The absolute temperature (Kelvin) scale can be understood loosely as a measure of average kinetic energy. Usually, system temperatures are positive. However, in particular isolated systems, the temperature defined in terms of Boltzmann's entropy can become negative.
The possibility of negative temperatures was first predicted by Lars Onsager in 1949.
Onsager was investigating 2D vortices confined within a finite area, and realized that since their positions are not independent degrees of freedom from their momenta, the resulting phase space must also be bounded by the finite area. Bounded phase space is the essential property that allows for negative temperatures, and can occur in both classical and quantum systems. As shown by Onsager, a system with bounded phase space necessarily has a peak in the entropy as energy is increased. For energies exceeding the value where the peak occurs, the entropy decreases as energy increases, and high-energy states necessarily have negative Boltzmann temperature.
A system with a truly negative temperature on the Kelvin scale is hotter than any system with a positive temperature. If a negative-temperature system and a positive-temperature system come in contact, heat will flow from the negative- to the positive-temperature system. A standard example of such a system is population inversion in laser physics.
Temperature is loosely interpreted as the average kinetic energy of the system's particles. The existence of negative temperature, let alone negative temperature representing "hotter" systems than positive temperature, would seem paradoxical in this interpretation.
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