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 can 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.
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". Quantum effects appear if the concentration of particles satisfieswhere 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,
gi
The variance of this distribution
V(n)
For comparison, the average number of fermions with energy
\varepsiloni
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:
\bar{n}i=
gi | ||||||
|
\ll1
(\varepsiloni-\mu)/kBT | |
e |
\pm1\gg1
(\varepsiloni-\mu)/kBT | |
e |
\gg1
\bar{n}i ≈
gi | = | |||
|
1 | |
Z |
-(\varepsiloni-\mu)/kBT | |
e |
\varepsiloni-\mu\ggkBT
\bar{n}i=
gi | ||||||
|
\ll1
In addition to reducing to the Maxwell–Boltzmann distribution in the limit of high
T
\varepsiloni-\mu\llkBT
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.[2] [3]
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 d'Alembert known from his Croix ou Pile article[4] [5]). 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"[6] [7] 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 German: italic=yes|[[Zeitschrift für Physik]]. 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 German: italic=yes|Zeitschrift für Physik, 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.[8] 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.
In the microcanonical ensemble, one considers a system with fixed energy, volume, and number of particles. We take a system composed of identical bosons,
ni
\varepsiloni
gi
\varepsiloni
gi
\varepsiloni
ni
gi
ni
gi
i
m | |
C | |
k |
ni+gi-1 | |
C | |
ni |
The maximum number of arrangements determining the corresponding occupation number
ni
d(lnWBE)=0
ni\gg1
gi\gg1
ni/gi=O(1)
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.[9] 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.
Every single-particle state is of a fixed energy,
\varepsilon
N
N\varepsilon
E
N\varepsilon
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 and may be evaluated as such:
Note that the geometric series is convergent only if
(\mu-\varepsilon)/kBT | |
e |
<1
\varepsilon=0
\mu<0
The average particle number for that single-particle substate is given byThis result applies for each single-particle level and thus forms the Bose–Einstein distribution for the entire state of the system.[11] [12]
The variance in particle number, , is:
As a result, for highly occupied states the standard deviation of the particle number of an energy level is very large, slightly larger than the particle number itself:
\sigmaN ≈ \langleN\rangle
\langleN\rangle
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.[13] See also Müller-Kirsten.[14] The fluctuations of the ground state in the condensed region are however markedly different in the canonical and grand-canonical ensembles.[15]
Suppose we have a number of energy levels, labeled by index
i
\varepsiloni
ni
gi
gi
i
Let
w(n,g)
n
g
n
w(n,1)=1
(n+1)
n
With a little thought (see Notes below) it can be seen that the number of ways of distributing
n
Continuing this process, we can see that
w(n,g)
For example, the population numbers for two particles in three sublevels are 200, 110, 101, 020, 011, or 002 for a total of six which equals 4!/(2!2!). The number of ways that a set of occupation numbers
ni
ni\gg1
Following the same procedure used in deriving the Maxwell–Boltzmann statistics, we wish to find the set of
ni
W
ln(W)
ni
Using the
ni\gg1
\left(x! ≈ xxe-x\sqrt{2\pix}\right)
ni
ni
ni
By a process similar to that outlined in the Maxwell–Boltzmann statistics article, it can be seen that:which, using Boltzmann's famous relationship
S=kBlnW
\beta=
1 | |
kBT |
\alpha=-
\mu | |
kBT |
\mu
Note that the above formula is sometimes written:where
z=\exp(\mu/kBT)
Also note that when the particle numbers are not conserved, removing the conservation of particle numbers constraint is equivalent to setting
\alpha
\mu
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 permutations 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 − 1) identical items will be:
See the image for a visual representation of one such distribution of n particles in g boxes that can be represented as partitions.
OR
The purpose of these notes is to clarify some aspects of the derivation of the Bose–Einstein distribution for beginners. The enumeration of cases (or ways) in the Bose–Einstein distribution can be recast as follows. Consider a game of dice throwing in which there are
n
\{1,...,g\}
g\ge1
i
mi
(i-1)
mi-1
mi\gemi-1
(m1,m2,...,mn)
mi\gemi-1
S(n,g)
Then the quantity
w(n,g)
n
g
S(n,g)
S(n,g)
w(n,g)
S(n,g)
Example n = 4, g = 3: (there are
15
S(4,3)
Subset
(a)
mi
1
mn
1
g=3
(b)
m1=m2=1
m3
2
g=3
mi\gemi-1
S(n,g)
m4
\left\{2,3\right\}
(c)
(d)
Each element of
S(4,3)
n=4
\left\{1,2,3\right\}
g=3
More generally, each element of
S(n,g)
n
\left\{1,...,g\right\}
g
w(n,g)
w(n,g)
To understand the decompositionor for example,
n=4
g=3
let us rearrange the elements of
S(4,3)
Clearly, the subset
(\alpha)
S(4,3)
By deleting the index
m4=3
(\beta)
S(4,3)
In other words, there is a one-to-one correspondence between the subset
(\beta)
S(4,3)
S(3,2)
Similarly, it is easy to see that
Thus we can write or more generally,and since the setsare non-intersecting, we thus havewith the convention thatContinuing the process, we arrive at the following formulaUsing the convention (7)2 above, we obtain the formulakeeping in mind that for
q
p
It can then be verified that (8) and (2) give the same result for
w(4,3)
w(3,3)
w(3,2)
See main article: article and Bose–Einstein condensation (network theory). Viewed as a pure probability distribution, the Bose–Einstein distribution has found application in other fields: