Ensemble Theory and Microcanonical Ensemble

Carlos Roberto Valdivia Garca

Divisin de Ciencias e Ingenieras Campus Len, Universidad de Guanajuato,

Loma del Bosque 103, 37150 Len Guanajuato, Mxico

(Dated: August 27, 2014)

I.

PHASE-SPACE DENSITY, ERGODIC HYPOTHESIS

In the preceding sections we have seen how one can-at least in principle-calculate the macroscopic properties of
a closed system for given E,V, and N. We now want to develop a more general formalism which we can also use to
describe dierent situations (e.g., a system at a given temperature in a heat bath). In a given macrostate a system
can assume a large number of concrete microstates.

In the case of a closed system all possible microstates lie on

the energy surface. Up to now, all these microstates in principle have been assumed to be equally likely: We have
assumed that all microstates of the energy surface of a closed system can be assumed with equal probability.
This assumption is the basic postulate of statistical mechanics. For nonclosed systems, however, it could very well
be true that microstates with a certain enegy are more probable than microstates with another energy.
microstates may no longer be counted equally, but must be multiplied by a weighting funtion
on the energy of the state. To each phase-space point

(qv , pv ),

therefore, a weight

(qv , pv )

(qv , pv )

Then the

which depends

is attached, which can

be interppreted as the probability density for the macrosystem to reach this phase-space point. Thus, for a closed
system

would vanish outside the energy surfaccce, and it would assume a constant value on the energy surface.

The probability density

is called the phase-space density. It can be normalized to 1, f(qv , pv )

d3N q d3N p (qv , pv ) = 1

(6.1)

If now f(qv,pv) is any observable of the system,

e.g.,

the total energy H(qv,pv) or the angular momentum

L(vector)(qv.pv), then in general one will observe a mean value (f ) of this quantity in a given macrostate, in which
each microstate (qv, pv) contributes corresponding to its weight p(qv, pv): EQ2 Since each phase-space point (qv,
pv) can be identied with a copy of the actual macroscopic system in a certain microstate, Equation (6.2) just is an
average over a set of such identical copies (at a xed time). the quantity (F) is thus called the ensemble avergae of
the quantity f and the phase-space density p is the weighting funtion of the ensemble. In the case of a Closed system,
p is given by EQ3 The s-funtion ensures that all points which are not on the energy surface with the area o(E)
have the weight 0, while the factor 1/o is for normalization. the phase-space density of a closed system corresponds
to a certain ensemble of posssible microstates and is called a microcanonical ensemble, which we denoted by the
index mc. Other systems will, of course, have dierent phase-space densities, which we still have to calculate. For
practical calculations, however, Equation(6.3) is very inconvenient because of the s-funtion, which has a complicated
argument. As in the preceding sections, it is therefore better to allow for a small energy uncertainty DeltaE. One sets
EQ4 The constant in this case is determined by normalization, EQ5 This integral, however, is well known to us (cf.
Equation(5.65)), and we have (without the Gibbs factor 1/N!) EQ6 Since the factor H3N will appear very frequently,
from now on we will include it in the volume element of phase space. (Recall that the Gibbs correction factor appears
only i one afterwards corrects for the indistinguishability of the particles.)

from now on instead of Equation(6.1)

we will write EQ7 and, respectively, for Equation (6.2), EQ8 This has the advantage that the phase-space density
now is a dimensionless number.

The phase-space density of the microcanonical ensemble reads, nornalized (again

without Gibbs's factor): EQ9 Basic to ensemble theory is the further assumption that all thermodynamic quantities
of state can be written as an ensemble average of a suitable microscopic observable f(qv, pv). In the following we must

Electronic

address:

valdiviagc2014@licifug.ugto.mx

therefore not only determine the phase-space density for a nonclosed system, but also the function f(qv, pv), which
corresponds to a certain quantity of state. First, however, we want to pursue some eneral considerations concerning
the ensemble average. Up to now, we have started from some basic assumptions which cannot be directly derived from
classical mechanics. On the other hand, the solution of Hamilton's equations of motion of a system (qv(t),pv(t)) as
a function of time should uniquely x all imaginable observables of the system. However, the time dependence of the
actual phase-space trajectory is of no importance for the ensemble average. Instead, we have just related a probability
to each phase-space point(qv, pv) that this special microstate can be reached. Now in equilibrium, all thermodynamic
(macroscopical) observables are independent of time. In principle, these quantities therefore should be calculable as
a time average of the real phase-space trajectory, for instance, according to EQ10 where the time dependence (qv(t),
pv(t))is xed by Hamilton's equations of motion. The time average along the phase-space trajectory is of no essential
practical value, since for its calculation the complete solution of the equations of motion is needed. However, it is
of principle sifnicance.

Namely, if one could mathematically prove that the time average essentially leads to the

same result as the ensemble average, then our preceding assumptions could be founded purely microscopically. The
time average f  and the ensemble average (f ) for a closed system at a given energy would certainly be identical if
during its time evolution the phase-space trajectory passed through each point of the energy surface an equal number
of times (e.g., once-sucient condition). This condition, which was introduced by Boltzmann in 1871, is called the
ergodic hypothesis. In this case, an average over all times, of course, would exactly correspond to an average over
all points of the surface with equal weights. That such ergodic systems exist, in principle, is shown by our example
of the one-dimensional harmonic oscillator. As we know, during one period each point of the energy ellipse is passed
is passed just once. For higher dimensional systems, however, one can prove mathematically that the phase-space
trajectory, in principle, can never pass through all points of the energy surface. The reason for this is that on the one
hand Hamilton's equations of motion always have a unique solution, so that the phase-space trajectory can never cross
itself, but that on the other hand it is problematic to map a one-dimensional time interval onto an N-dimensional
surface element. Now for the identity of time averages and ensemble averages, it is not necessary that the phase-space
trajectory really pass through every point of the energy surface. It would also be sucient if it came arbitrarily close to
each point. This assumption is the so-called quasi ergodic hypothesis. Unfortunately, up to now all attempts to base
ensemble theory strictly on classical mechanics have failed. Therefore, we must pose our assumptions axiomatically
at the starting point of statistical mechanics.

A.

Una ecuacin relacionada con la cantidad

Jion

Una subseccin

se puede escribir como:

Jion

 a
exp E
kT
=A

kT

(1)

dicha ecuacin puede ser referida usando (1) o (1). Una ecuacin sin numerar se puede escribir como

 r
X r2
X ri
X
X
S
i
i
=
=2
=2
.
ri
yi
Jil l
j

j
j
j
i
i
i
l

Para escribir una direccin electrnica se usa.

http://www.world.universe.

Infandum, regina, iubes renovare dolorem, Troianas ut opes et lamentabile regnum cruerint Danai; quaeque ipse
miserrima vidi, et quorum pars magna fui. Quis talia fando Myrmidonum Dolopumve aut duri miles Ulixi temperet
a lacrimis?
Prueba de una lista.
1. Lista con ms de una lnea.

Una subentrada.

2. Lnea nal

II.

A continuacin un ejemplo de gura en FIG. 1

TEORA

Figure 2: Ejemplo de gura con un ancho jo de 4 pulgadas

Figure 1: Pie de gura, con la proporcin ja al 40% de la altura una pagina.

III.

MONTAJE EXPERIMENTAL

IV.

RESULTADOS

Table I: Ejemplo de una tabla en LATEX.

Cu
Ag
Au
Mg
Zn
Cd
Hg
Al
Ga
In
Tl

rc
0.900
0.990
1.150
0.490
0.300
0.530
0.550
0.230
0.310
0.460
0.480

r0
14.10
15.90
15.90
17.60
15.20
17.10
17.80
15.80
16.70
18.40
18.90

r0
2.550
2.710
2.710
3.200
2.970
3.160
3.220
3.240
3.330
3.500
3.55

Otro ejemplo de tabla viene dado en la tabla II

Damping Integral I
Dierence vs real value
1.0
4.311989078
1.769188798 108
0.1
625.7265817
1.769182584 108
0.01
68162.14831
1.768507220 108
6
0.001
6.803315298 10 1.701155688 108
0.0005
2.720247713 107 1.497164070 108
0.0002
1.699703007 108 6.9485834 106
0.00015
3.021553033 108 1.252364192 107
0.0001
6.798171231 108 5.028982390 108
Table II: Values of the integral obtained for dierent values of the damping parameter. In the third column, the dierence
between calculated value and the value obtained for HCMY approach, are shown.

V.

CONCLUSIONES

Figure 3: Otro ejemplo de gura con una escala de 15% del tamao real

[1] H.B. Callen, Thermodynamics and an Introduction to Thermostatistics. Ed. John Willey & Sons (New York, 1985) pp 35.
[2] N.F. Carnahan & K.E. Starling, J. Chem. Phys. 51 (1969) 635636.