Microcanonical ensemble

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In statistical mechanics, a microcanonical ensemble is the statistical ensemble that is used to represent the
possible states of a mechanical system which has an exactly specified total energy.[1] The system is assumed to
be isolated in the sense that the system cannot exchange energy or particles with its environment, so that (by
conservation of energy) the energy of the system remains exactly known as time goes on. The system's energy,
composition, volume, and shape are kept the same in all possible states of the system.

The macroscopic variables of the microcanonical ensemble are quantities that influence the nature of the
system's internal states such as the total number of particles in the system (symbol: N), the system's volume
(symbol: V), as well as the total energy in the system (symbol: E). This ensemble is therefore sometimes called
the NVE ensemble, as each of these three quantities is a constant of the ensemble.

In simple terms, the microcanonical ensemble is defined by assigning an equal probability to every microstate
whose energy falls within a range centered at E. All other microstates are given a probability of zero. Since the
probabilities must add up to 1, the probability P is the inverse of the number of microstates W within the range
of energy,

The range of energy is then reduced in width until it is infinitesimally narrow, still centered at E. In the limit of
this process, the microcanonical ensemble is obtained.[1]

Contents
1 Applicability
2 Properties
3 Thermodynamic analogies
4 Precise expressions for the ensemble
4.1 Quantum mechanical
4.2 Classical mechanical
5 Notes
6 References

Applicability
The microcanonical ensemble is sometimes considered to be the fundamental distribution of statistical
thermodynamics, as its form can be justified on elementary grounds such as the principle of indifference: the
microcanonical ensemble describes the possible states of an isolated mechanical system when the energy is
known exactly, but without any more information about the internal state. Also, in some special systems the
evolution is ergodic in which case the microcanonical ensemble is equal to the time-ensemble when starting out
with a single state of energy E (a time-ensemble is the ensemble formed of all future states evolved from a
single initial state).

In practice, the microcanonical ensemble does not correspond to an experimentally realistic situation. With a
real physical system there is at least some uncertainty in energy, due to uncontrolled factors in the preparation
of the system. Besides the difficulty of finding an experimental analogue, it is difficult to carry out calculations
that satisfy exactly the requirement of fixed energy since it prevents logically independent parts of the system
from being analyzed separately. Moreover there are ambiguities regarding the appropriate definitions of
quantities such as entropy and temperature in the microcanonical ensemble.[1]

Systems in thermal equilibrium with their environment have uncertainty in energy, and are instead described by
the canonical ensemble or the grand canonical ensemble, the latter if the system is also in equilibrium with its
environment in respect to particle exchange.

Properties
Statistical equilibrium (steady state): A microcanonical ensemble does not evolve over time, despite the
fact that every constituent of the ensemble is in motion. This is because the ensemble is defined strictly
as a function of a conserved quantity of the system (energy).[1]
Maximum information entropy: For a given mechanical system (fixed N, V) and a given range of energy,
the uniform distribution of probability over microstates (as in the microcanonical ensemble) maximizes
the ensemble average log P.[1]
Three different quantities called "entropy" can be defined for the microcanonical ensemble.[2] Each can
be defined in terms of the phase volume function v(E) which counts the total number of states with
energy less than E (see the Precise expressions section for the mathematical definition of v)
the Boltzmann entropy[note 1]

the volume entropy

the surface entropy

Different "temperatures" may be defined by differentiating the entropy quantities

.
.

The analogies between these quantities and thermodynamics is not perfect, as discussed below.

Thermodynamic analogies
Early work in statistical mechanics by Ludwig Boltzmann led to his eponymous entropy equation for a system
of a given total energy, S = k log W, where W is the number of distinct states accessible by the system at that
energy. Boltzmann did not elaborate too deeply on what exactly constitutes the set of distinct states of a system,
besides the special case of an ideal gas. This topic was investigated to completion by Josiah Willard Gibbs who
developed the generalized statistical mechanics for arbitrary mechanical systems, and defined the
microcanonical ensemble described in this article.[1] Gibbs investigated carefully the analogies between the
microcanonical ensemble and thermodynamics, especially how they break down in the case of systems of few
degrees of freedom. He introduced two further definitions of microcanonical entropy that do not depend on -
the volume and surface entropy described above. (Note that the surface entropy differs from the Boltzmann
entropy only by an -dependent offset.)

The volume entropy S and associated T form a close analogy to thermodynamic entropy and temperature. It
The volume entropy Sv and associated Tv form a close analogy to thermodynamic entropy and temperature. It
is possible to show exactly that

(P is the ensemble average pressure) as expected for the first law of thermodynamics. A similar equation can
be found for the surface (Boltzmann) entropy and its associated Ts, however the "pressure" in this equation is a
complicated quantity unrelated to the average pressure.[1]

The microcanonical Tv and Ts are not entirely satisfactory in their analogy to temperature. Outside of the
thermodynamic limit, a number of artifacts occur.

Nontrivial result of combining two systems: Two systems, each described by an independent
microcanonical ensemble, can be brought into thermal contact and be allowed to equilibrate into a
combined system also described by a microcanonical ensemble. Unfortunately, the energy flow between
the two systems cannot be predicted based on the initial T's. Even when the initial T's are equal, there
may be energy transferred. Moreover, the T of the combination is different from the initial values. This
contradicts the intuition that temperature should be an intensive quantity, and that two equal-temperature
systems should be unaffected by being brought into thermal contact.[1]
Strange behaviour for few-particle systems: Many results such as the microcanonical equipartition
theorem acquire a one- or two-degree of freedom offset when written in terms of Ts. For a small systems
this offset is significant, and so if we make Ss the analogue of entropy, several exceptions need to be
made for systems with only one or two degrees of freedom.[1]
Spurious negative temperatures: A negative Ts occurs whenever the density of states is decreasing with
energy. In some systems the density of states is not monotonic in energy, and so Ts can change sign
multiple times as the energy is increased.[3][4]

The preferred solution to these problems is avoid use of the microcanonical ensemble. In many realistic cases a
system is thermostatted to a heat bath so that the energy is not precisely known. Then, a more accurate
description is the canonical ensemble or grand canonical ensemble, both of which have complete
correspondence to thermodynamics.[5]

Precise expressions for the ensemble

The precise mathematical expression for a statistical ensemble depends on the kind of mechanics under
considerationquantum or classicalsince the notion of a "microstate" is considerably different in these two
cases. In quantum mechanics, diagonalization provides a discrete set of microstates with specific energies. The
classical mechanical case involves instead an integral over canonical phase space, and the size of microstates in
phase space can be chosen somewhat arbitrarily.

To construct the microcanonical ensemble, it is necessary in both types of mechanics to first specify a range of
energy. In the expressions below the function (a function of H, peaking at E with width ) will be
used to represent the range of energy in which to include states. An example of this function would be[1]

or, more smoothly,

Quantum mechanical
A statistical ensemble in quantum
mechanics is represented by a Example of microcanonical ensemble for a quantum system
density matrix, denoted by . The consisting of one particle in a potential well.
microcanonical ensemble can be
written using braket notation, in
terms of the system's energy
eigenstates and energy eigenvalues.
Given a complete basis of energy
eigenstates |i, indexed by i, the
microcanonical ensemble is:

Plot of all possible states of this An ensemble containing only those

system. The available stationary states states within a narrow interval of
displayed as horizontal bars of energy. As the energy width is taken
varying darkness according to to zero, a microcanonical ensemble is
|i(x)|2. obtained (provided the interval
contains at least one state).
The particle's Hamiltonian is Schrdinger-type, = U(x) + p2/2m (the potential U(x) is
plotted as a red curve). Each panel shows an energy-position plot with the various
stationary states, along with a side plot showing the distribution of states in energy.

where the Hi are the energy eigenvalues determined by |i = Hi|i (here is the system's total energy
operator, i. e., Hamiltonian operator). The value of W is determined by demanding that is a normalized
density matrix, and so

The state volume function (used to calculate entropy) is given by

The microcanonical ensemble is defined by taking the limit of the density matrix as the energy width goes to
zero, however a problematic situation occurs once the energy width becomes smaller than the spacing between
energy levels. For very small energy width, the ensemble does not exist at all for most values of E since no
states fall within the range. When the ensemble does exist it typically only contains one (or two) states, since in
a complex system the energy levels are only ever equal by accident (see random matrix theory for more
discussion on this point). Moreover, the state volume function also increases only in discrete increments and so
its derivative is only ever infinite or zero, making it difficult to define the density of states. This problem can be
solved by not taking the energy range completely to zero and smoothing the state volume function, however
this makes the definition of the ensemble more complicated since it becomes then necessary to specify the
energy range in addition to other variables (together, an NVE ensemble).

Classical mechanical
In classical mechanics, an ensemble
Example of microcanonical ensemble for a classical system consisting
is represented by a joint probability
of one particle in a potential well.
density function
(p1, pn, q1, qn) defined
over the system's phase space.[1] The
phase space has n generalized
coordinates called q1, qn, and n
associated canonical momenta called
p1, pn.

The probability density function for

the microcanonical ensemble is:

where

H is the total energy

(Hamiltonian) of the system, a
function of the phase
(p1, qn),
h is an arbitrary but
predetermined constant with
the units of energytime ,
setting the extent of one
microstate and providing
correct dimensions to .[note 2]
C is an overcounting
correction factor, often used
for particle systems where
identical particles are able to
change place with each other.[note 3]
Plot of all possible states of this An ensemble restricted to only those
system. The available physical states states within a narrow interval of
are evenly distributed in phase space, energy. This ensemble appears as a
but with an uneven distribution in thin shell in phase space. As the
energy; the side-plot displays dv/dE. energy width is taken to zero, a
microcanonical ensemble is obtained.
Each panel shows phase space (upper graph) and energy-position space (lower
graph). The particle's Hamiltonian is H = U(x) + p2/2m, with the potential
U(x) shown as a red curve. The side plot shows the distribution of states in
energy.

Again, the value of W is determined by demanding that is a normalized probability density function:

This integral is taken over the entire phase space. The state volume function (used to calculate entropy) is
defined by

As the energy width is taken to zero, the value of W decreases in proportion to as W = (dv/dE).

Based on the above definition, the microcanonical ensemble can be visualized as an infinitesimally thin shell in
phase space, centered on a constant-energy surface. Although the microcanonical ensemble is confined to this
surface, it is not necessarily uniformly distributed over that surface: if the gradient of energy in phase space
varies, then the microcanonical ensemble is "thicker" (more concentrated) in some parts of the surface than
others. This feature is an unavoidable consequence of requiring that the microcanonical ensemble is a steady-
state ensemble.
Notes
1. SB is the information entropyor Gibbs entropy for the specific case of the microcanonical ensemble. Note that it
depends on the energy width .
fectively set h = 1 [energy unit][time unit], leading to unit-
2. (Historical note) Gibbs' original ensemble ef
dependence in the values of some thermodynamic quantities like entropy and chemical potential. Since the advent of
quantum mechanics,h is often taken to be equal toPlanck's constant in order to obtain a semiclassical correspondence
with quantum mechanics.
3. In a system of N identical particles, C = N! (factorial of N). This factor corrects the overcounting in phase space due to
identical physical states being found in multiple locations. See thestatistical ensemble article for more information on
this overcounting.

References
1. Gibbs, Josiah Willard (1902). Elementary Principles in Statistical Mechanics
. New York: Charles Scribner's Sons.
2. Huang, Kerson (1987).Statistical Mechanics. Wiley. p. 134. ISBN 0471815187.
3. Jrn Dunkel; Stefan Hilbert (2013). "Inconsistent thermostatistics and negative absolute temperatures".
arXiv:1304.2066
[cond-mat.stat-mech].
4. See further references athttps://sites.google.com/site/entropysurfaceorvolume/
5. Tolman, R. C. (1938).The Principles of Statistical Mechanics. Oxford University Press.

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Categories: Statistical ensembles

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