right|thumb|250px|[[International System of Units|SI temperature/coldness conversion scale: Temperatures on the Kelvin scale are shown in blue (Celsius scale in green, Fahrenheit scale in red), coldness values in gigabyte per nanojoule are shown in black. Infinite temperature (coldness zero) is shown at the top of the diagram; positive values of coldness/temperature are on the right-hand side, negative values on the left-hand side.]]
Certain thermodynamic 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. 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.
Thermodynamic systems with unbounded phase space cannot achieve negative temperatures: adding heat always increases their entropy. The possibility of a decrease in entropy as energy increases requires the system to "saturate" in entropy. This is only possible if the number of high energy states is limited. For a system of ordinary (quantum or classical) particles such as atoms or dust, the number of high energy states is unlimited (particle momenta can in principle be increased indefinitely). Some systems, however (see the examples below), have a maximum amount of energy that they can hold, and as they approach that maximum energy their entropy actually begins to decrease.
History
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.
The limited range of states accessible to a system with negative temperature means that negative temperature is associated with emergent ordering of the system at high energies. For example in Onsager's point-vortex analysis negative temperature is associated with the emergence of large-scale clusters of vortices. They wrote:
: A system in a negative temperature state is not cold, but very hot, giving up energy to any system at positive temperature put into contact with it. It decays to a normal state through infinite temperature.
Definition of temperature
The absolute temperature (Kelvin) scale can be 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. The paradox is resolved by considering the more rigorous definition of thermodynamic temperature in terms of Boltzmann's entropy formula. This reveals the tradeoff between internal energy and entropy contained in the system, with "coldness", the reciprocal of temperature, being the more fundamental quantity. Systems with a positive temperature will increase in entropy as one adds energy to the system, while systems with a negative temperature will decrease in entropy as one adds energy to the system.
The definition of thermodynamic temperature is a function of the change in the system's entropy under reversible heat transfer :
: <math>T = \frac{dQ_\mathrm{rev{dS}.</math>
Entropy being a state function, the integral of over any cyclical process is zero. For a system in which the entropy is purely a function of the system's energy , the temperature can be defined as:
: <math> T = \left( \frac{dS}{dE} \right)^{-1}.</math>
Equivalently, thermodynamic beta, or "coldness", is defined as
:<math>\beta = \frac{1}{kT} = \frac{1}{k} \frac{dS}{dE},</math>
where is the Boltzmann constant.
Note that in classical thermodynamics, is defined in terms of temperature. This is reversed here, is the statistical entropy, a function of the possible microstates of the system, and temperature conveys information on the distribution of energy levels among the possible microstates. For systems with many degrees of freedom, the statistical and thermodynamic definitions of entropy are generally consistent with each other.
Some theorists have proposed using an alternative definition of entropy as a way to resolve perceived inconsistencies between statistical and thermodynamic entropy for small systems and systems where the number of states decreases with energy, and the temperatures derived from these entropies are different. It has been argued that the new definition would create other inconsistencies; its proponents have argued that this is only apparent. This is a consequence of the definition of temperature in statistical mechanics for systems with limited states. By injecting energy into these systems in the right fashion, it is possible to create a system in which there are more particles in the higher energy states than in the lower ones. The system can then be characterized as having a negative temperature.
A substance with a negative temperature is not colder than absolute zero, but rather it is hotter than infinite temperature.
The corresponding inverse temperature scale, for the quantity (where is the Boltzmann constant), runs continuously from low energy to high as +∞, …, 0, …, −∞. Because it avoids the abrupt jump from +∞ to −∞, is considered more natural than . Although a system can have multiple negative temperature regions and thus have −∞ to +∞ discontinuities.
In many familiar physical systems, temperature is associated to the kinetic energy of atoms. Since there is no upper bound on the momentum of an atom, there is no upper bound to the number of energy states available when more energy is added, and therefore no way to get to a negative temperature. This allows the experiment to be run as a variation of nuclear magnetic resonance spectroscopy. In the case of electronic and nuclear spin systems, there are only a finite number of modes available, often just two, corresponding to spin up and spin down. In the absence of a magnetic field, these spin states are degenerate, meaning that they correspond to the same energy. When an external magnetic field is applied, the energy levels are split, since those spin states that are aligned with the magnetic field will have a different energy from those that are anti-parallel to it.
In the absence of a magnetic field, such a two-spin system would have maximum entropy when half the atoms are in the spin-up state and half are in the spin-down state, and so one would expect to find the system with close to an equal distribution of spins. Upon application of a magnetic field, some of the atoms will tend to align so as to minimize the energy of the system, thus slightly more atoms should be in the lower-energy state (for the purposes of this example we will assume the spin-down state is the lower-energy state). It is possible to add energy to the spin system using radio frequency techniques. This causes atoms to flip from spin-down to spin-up.
Since we started with over half the atoms in the spin-down state, this initially drives the system towards a 50/50 mixture, so the entropy is increasing, corresponding to a positive temperature. However, at some point, more than half of the spins are in the spin-up position. In this case, adding additional energy reduces the entropy, since it moves the system further from a 50/50 mixture. This reduction in entropy with the addition of energy corresponds to a negative temperature.
In NMR spectroscopy, such spin flips correspond to pulses with pulse widths over 180° (for a given spin). While relaxation is fast in solids, it can take several seconds in solutions and even longer in gases and in ultracold systems; several hours were reported for silver and rhodium at picokelvin temperatures.
Motional degrees of freedom
Negative temperatures have also been achieved in motional degrees of freedom. Using an optical lattice, upper bounds were placed on the kinetic energy, interaction energy and potential energy of cold potassium-39 atoms. This was done by tuning the interactions of the atoms from repulsive to attractive using a Feshbach resonance and changing the overall harmonic potential from trapping to anti-trapping, thus transforming the Bose–Hubbard Hamiltonian from . Performing this transformation adiabatically while keeping the atoms in the Mott insulator regime, it is possible to go from a low entropy positive temperature state to a low entropy negative temperature state. In the negative temperature state, the atoms macroscopically occupy the maximum momentum state of the lattice. The negative temperature ensembles equilibrated and showed long lifetimes in an anti-trapping harmonic potential.
Two-dimensional vortex motion
The two-dimensional systems of vortices confined to a finite area can form thermal equilibrium states at negative temperature, and indeed negative temperature states were first predicted by Onsager in his analysis of classical point vortices. Onsager's prediction was confirmed experimentally for a system of quantum vortices in a Bose–Einstein condensate in 2019.
See also
- Negative resistance