Wikipedia / Bose–Einstein statistics
Wikipedia / Bose–Einstein statistics
In quantum statistics, Bose–Einstein statistics (B–E statistics) describes one of two possible ways in which a collection of non-interacting identical particles may occupy a set of available discrete energy states at thermodynamic equilibrium. The aggregation of particles in the same state, which is a characteristic of particles obeying Bose–Einstein statistics, accounts for the cohesive streaming of laser light and the frictionless creeping of superfluid helium. The theory of this behaviour was developed (1924–25) by Satyendra Nath Bose, who recognized that a collection of identical and indistinguishable particles could be distributed in this way. The idea was later adopted and extended by Albert Einstein in collaboration with Bose.
Bose–Einstein statistics apply only to particles that do not follow the Pauli exclusion principle restrictions. Particles that follow Bose-Einstein statistics are called bosons, which have integer values of spin. In contrast, particles that follow Fermi-Dirac statistics are called fermions and have half-integer spins.
Bose–Einstein distribution
At low temperatures, bosons behave differently from fermions (which obey the Fermi–Dirac statistics) in a way that an unlimited number of them can "condense" into the same energy state. This apparently unusual property also gives rise to the special state of matter the Bose–Einstein condensate. Fermi–Dirac and Bose–Einstein statistics apply when quantum effects are important and the particles are "indistinguishable where is the number of particles, is the volume, and is the quantum concentration, for which the interparticle distance is equal to the thermal de Broglie wavelength, so that the wavefunctions of the particles are barely overlapping.
Fermi–Dirac statistics applies to fermions (particles that obey the Pauli exclusion principle), and Bose–Einstein statistics applies to bosons. As the quantum concentration depends on temperature, most systems at high temperatures obey the classical (Maxwell–Boltzmann) limit, unless they also have a very high density, as for a white dwarf. Both Fermi–Dirac and Bose–Einstein become Maxwell–Boltzmann statistics at high temperature or at low concentration.
Bose–Einstein statistics was introduced for photons in 1924 by Bose and generalized to atoms by Einstein in 1924–25.
The expected number of particles in an energy state for Bose–Einstein statistics is: with and where is the occupation number (the number of particles) in state is the degeneracy of energy level , is the energy of the th state, μ is the chemical potential (zero for a photon gas), is the Boltzmann constant, and is the absolute temperature.
is calculated directly from the expression above for the average number.
given by Fermi–Dirac particle-energy distribution
As mentioned above, both the Bose–Einstein distribution and the Fermi–Dirac distribution approaches the Maxwell–Boltzmann distribution in the limit of high temperature and low particle density, without the need for any ad hoc assumptions:
, which is the result from Maxwell–Boltzmann statistics.
. This again reduces to Maxwell–Boltzmann statistics.
In addition to reducing to the Maxwell–Boltzmann distribution and low density, Bose–Einstein statistics also reduces to Rayleigh–Jeans law
History
In 1900, Max Planck derived the Planck law to explain blackbody radiation. For this purpose, he introduced the concept of quanta of energy.
Władysław Natanson in 1911 concluded that Planck's law requires indistinguishability of "units of energy", although he did not frame this in terms of Einstein's light quanta.
While presenting a lecture at the University of Dhaka (in what was then British India and is now Bangladesh) on the theory of radiation and the ultraviolet catastrophe, Satyendra Nath Bose intended to show his students that the contemporary theory was inadequate, because it predicted results not in accordance with experimental results. During this lecture, Bose committed an error in applying the theory, which unexpectedly gave a prediction that agreed with the experiment. The error was a simple mistake – similar to arguing that flipping two fair coins will produce two heads one-third of the time – that would appear obviously wrong to anyone with a basic understanding of statistics (remarkably, this error resembled the famous blunder by Jean le Rond d'Alembert known from his Croix ou Pile article). However, the results it predicted agreed with experiment, and Bose realized it might not be a mistake after all. For the first time, he took the position that the Maxwell–Boltzmann distribution would not be true for all microscopic particles at all scales. Thus, he studied the probability of finding particles in various states in phase space, where each state is a little patch having phase volume of h3, and the position and momentum of the particles are not kept particularly separate but are considered as one variable.
Bose adapted this lecture into a short article called "Planck's law and the hypothesis of light quanta" and submitted it to the Philosophical Magazine. However, the referee's report was negative, and the paper was rejected. Undaunted, he sent the manuscript to Albert Einstein requesting publication in the . Einstein immediately agreed, personally translated the article from English into German (Bose had earlier translated Einstein's article on the general theory of relativity from German to English), and saw to it that it was published. Bose's theory achieved respect when Einstein sent his own paper in support of Bose's to , asking that they be published together. The paper came out in 1924.
The reason Bose produced accurate results was that since photons are indistinguishable from each other, one cannot treat any two photons having equal quantum numbers (e.g., polarization and momentum vector) as being two distinct identifiable photons. Bose originally had a factor of 2 for the possible spin states, but Einstein changed it to polarization. By analogy, if in an alternate universe coins were to behave like photons and other bosons, the probability of producing two heads would indeed be one-third, and so is the probability of getting a head and a tail which equals one-half for the conventional (classical, distinguishable) coins. Bose's "error" leads to what is now called Bose–Einstein statistics.
Bose and Einstein extended the idea to atoms and this led to the prediction of the existence of phenomena which became known as Bose–Einstein condensate, a dense collection of bosons (which are particles with integer spin, named after Bose), which was demonstrated to exist by experiment in 1995.
Derivation
Derivation from the microcanonical ensemble
In the microcanonical ensemble states is a problem of combinatoricsth energy level), where each box is capable of containing an infinite number of bosons (because for bosons the Pauli exclusion principle does not apply), would be (see image): is the k-combination of a set with m
can be simplified using Stirling's approximation to
The entropy of the system can then be expressed as
The three constraints we can impose on the system can be expressed as
(conservation of N),
(conservation of E), and
(second law of thermodynamics for a system at equilibrium).
:
Now we can write
for which to be true, it must be the case that for any i
and simplifying we obtain
reduces to
which is the form of the Bose-Einstein distribution. Note that this form holds even for a system of interacting bosons.
Derivation from the grand canonical ensemble
The Bose–Einstein distribution, which applies only to a quantum system of non-interacting bosons, is naturally derived from the grand canonical ensemble without any approximations. In this ensemble, the system is able to exchange energy and exchange particles with a reservoir (temperature T and chemical potential μ fixed by the reservoir).
Due to the non-interacting quality, each available single-particle level (with energy level ϵ) forms a separate thermodynamic system in contact with the reservoir. That is, the number of particles within the overall system that occupy a given single particle state form a sub-ensemble that is also grand canonical ensemble; hence, it may be analysed through the construction of a grand partition function.
This formula applies to fermionic systems as well as bosonic systems. Fermi–Dirac statistics arises when considering the effect of the Pauli exclusion principle: whilst the number of fermions occupying the same single-particle state can only be either 1 or 0, the number of bosons occupying a single particle state may be any integer. Thus, the grand partition function for bosons can be considered a geometric series
, whereas the Fermi gas is allowed to take both positive and negative values for the chemical potential.
This result applies for each single-particle level and thus forms the Bose–Einstein distribution for the entire state of the system.
The variance
As a result, for highly occupied states the standard deviation. This large uncertainty is due to the fact that the probability distribution for the number of bosons in a given energy level is a geometric distribution; somewhat counterintuitively, the most probable value for N is always 0. (In contrast, classical particles have instead a Poisson distribution, and with the most-probable N.)
Derivation in the canonical approach
It is also possible to derive approximate Bose–Einstein statistics in the canonical ensemble. These derivations are lengthy and only yield the above results in the asymptotic limit of a large number of particles. The reason is that the total number of bosons is fixed in the canonical ensemble. The Bose–Einstein distribution in this case can be derived as in most texts by maximization, but the mathematically best derivation is by the Darwin–Fowler method of mean values as emphasized by Dingle. See also Müller-Kirsten. The fluctuations of the ground state in the condensed region are however markedly different in the canonical and grand-canonical ensembles.
is called the "degeneracy" of that energy level. Any number of bosons can occupy the same sublevel.
Let
With a little thought (see Notes where we have used the following theorem involving binomial coefficients
is just a binomial coefficient (See Notes
.
Following the same procedure used in deriving the Maxwell–Boltzmann statistics for which W and, since it is easier to accomplish mathematically, we will maximise the latter function instead. We constrain our solution using Lagrange multipliers
approximation and using Stirling's approximation where K
By a process similar to that outlined in the Maxwell–Boltzmann statistics becomes a statement of the second law of thermodynamics where S is the entropy is the chemical potential, kB is the Boltzmann constant and T is the temperature
is the absolute activity, as noted by McQuarrie.
to zero. This will be the case for photons and massive particles in mutual equilibrium and the resulting distribution will be the Planck distribution.
A much simpler way to think of Bose–Einstein distribution function is to consider that n particles are denoted by identical balls and g shells are marked by g-1 line partitions. It is clear that the permutationss of these n balls and g−1 partitions will give different ways of arranging bosons in different energy levels. Say, for 3 (=n) particles and 3 (=g) shells, therefore , the arrangement might be |●●|●, or ||●●●, or |●|●● , etc. Hence the number of distinct permutations of objects which have n identical items and (g−
See the image for a visual representation of one such distribution of n particles in g boxes that can be represented as partitions.
OR
, has to be greater than or equal to. Thus a valid sequence of die throws can be described by an n denote the set of these valid n-tuples:
(defined above, i.e., the number of elements (or valid n.
Example n = 4, g = 3:)
follows in the same manner.
can be thought of as a multiset, and the number of such multisets is the multiset coefficient
is a multiset is the multiset coefficient which is exactly the same as the formula, as derived above with the aid of a theorem involving binomial coefficients, namely
To understand the decomposition
(shown in red with double underline
or more generally, are non-intersecting, we thus have with the convention that Using the convention (7)2 above, we obtain the formula being constants, we have
, etc.
Interdisciplinary applications
Viewed as a pure probability distribution, the Bose–Einstein distribution has found application in other fields:
In recent years, Bose–Einstein statistics has also been used as a method for term weighting in information retrieval. The method is one of a collection of DFR ("Divergence From Randomness") models, the basic notion being that Bose–Einstein statistics may be a useful indicator in cases where a particular term and a particular document have a significant relationship that would not have occurred purely by chance. Source code for implementing this model is available from the Terrier project at the University of Glasgow.
The evolution of many complex systems, including the World Wide Web, business, and citation networks, is encoded in the dynamic web describing the interactions between the system's constituents. Despite their irreversible and nonequilibrium nature these networks follow Bose statistics and can undergo Bose–Einstein condensation. Addressing the dynamical properties of these nonequilibrium systems within the framework of equilibrium quantum gases predicts that the "first-mover-advantage", "fit-get-rich" (FGR) and "winner-takes-all" phenomena observed in competitive systems are thermodynamically distinct phases of the underlying evolving networks.
See also
Notes
References