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Introduction

H = kB T ij . zj

In classical Statistical Mechanics, one of the core results is the Virial Theorem: zi (1)

Here, the variable zi represents an arbitrary component of either the coordinates or momenta, and H is the Hamiltonian (Energy) function. The angle brackets indicate an average with respect to the measure associated with the underlying ensemble (or a time-average under assumptions of ergodicity). The symbols kB , T , and ij correspond to Boltzmanns constant, temperature, and the Kronecker Delta function respectively. Hence, the average is kB T if i equals j , but zero otherwise. It is remarkable how often the Virial Theorem is invoked in the literature with no statement of presupposition of conditions needed to ensure its truth. In this brief note we will present some proofs for the Virial Theorem, trying at all times to give careful statements of the assumptions invoked in each proof. In the rst two sections we give direct proofs of the Virial Theorem for unbounded systems under restraining potentials, and bounded systems with container walls. Both of these proofs are not (on the surface) applicable to systems on periodic domains (without the introduction of impulses). In the third section, we introduce the Equipartition Theorem, and a mechanical version of the Virial Theorem attributed to Clausius. We introduce a modied version of the Clausus Virial Theorem to account for systems on periodic domains.

Canonical Ensemble

In this section we will consider systems with bounded or unbounded domains, with the distribution of states governed by the canonical ensemble. In other words, the probability of nding the system in a state with conguration (q, p) = z is given by the probability density function: c (z ) exp 1 H (z ) . kB T

The constant of proportionality is determined so that the integral of over the entire domain is one. We will assume that each component zj is dened on the domain j with domain boundary j . We will also assume that the Hamiltonian is bounded below, which is the case in classical Molecular Dynamics. Some arguments can be made in the unbounded case (e.g., pure gravitation), but we will not consider that case here. 1

Lemma 1: Given a system governed by the canonical ensemble, with the properties

zj j

lim H (z ) = ,

and H (z ) > C0 , for some global constant C0 , the Virial Theorem holds. Proof: Applying the denition of the probability density function for the canonical ensemble to the average in the Virial theorem (1) results in the following: zi H 1 := zj C zi

z ,

H 1 exp H (z ) dz. zj kB T

(2)

exp

1 H (z ) dz. kB T

H kB T = zj C zj

zi

zj

exp

1 H (z ) kB T kB T C

dz,

zi exp

H (z ) kB T

dz +

zi H (z ) exp dz. zj kB T

Using the denition of C and zi /zj = ij reduces the relation to: zi H kB T = zj C zj zi exp H (z ) kB T dz + kB T ij .

Hence, the Virial Theorem holds: zi . We should note that in the case of classic periodic boundary conditions this proof only applies to components of the momenta. A dierent proof is required for components of the position, since the energy remains bounded as particles approach the edges of the simulation cell. H = kB T ij , zj

Microcanonical Ensemble

In this section we will consider systems with bounded or unbounded domains, with the distribution of states governed by the microcanonical ensemble. The direct proof of the Virial Theorem in this ensemble is very similar to the proof for the canonical ensemble. However, the assumptions are slightly more complicated, and we will require some additional relations from thermodynamics. In particular, we will assume that the temperature is dened through the entropy, S : S := kB ln 1 h3 N N ! (E H (z )) dz ,

(3)

S 1 := . T E

(4)

Here, the function is the unit (Heaviside) step-function, and the (h3N N !) is a normalization factor required to get the correct units and additivity properties for entropy. Recall that the probability of nding the system in a state with conguration (q, p) = z is given by the probability density function: mc (z ) [E H (z )] . The constant of proportionality is determined so that the integral of over the entire domain is one. We will assume that each component zj is dened on the domain j with domain boundary j . We will also assume that the Hamiltonian is bounded below, which is the case in classical Molecular Dynamics. Some arguments can be made in the unbounded case (e.g., pure gravitation), but we will not consider that case here. Lemma 2: Given a system governed by the microcanonical ensemble, with the property

zj j

lim H (z ) E,

with

zi i , i = j,

and H (z ) > C0 , for some global constant C0 , the Virial Theorem holds. Proof: Applying the denition of the probability density function for the microcanonical ensemble to the average in the Virial theorem (1) results in the following: zi 1 H := zj C zi

z ,

H [E H (z )] dz. zj

(5)

[E H (z )] dz.

Using the property that the delta-function is the derivative of the step-function yields: zi H 1 = zj C E zi

H [E H (z )] dz. zj

In the expression above the last term is zero, since the delta function is only nonzero when H (z ) = E , but at that point the integrand is zero. Using the assumption that the boundary of integration is inside of the boundary of the set H (z ) E , { [E H (z )] zi (E H (z ))} dz = 0, zj

since [E H (z )] = 0 on the boundary of j . Hence, we are left with the following expression: zi 1 H = ij zj C E (E H (z )) [E H (z )] dz.

1 C

(E H (z )) [E H (z )] dz.

The second term is zero, and the rst term can be rewritten as: zi H = ij zj ln E

1

[E H (z )] dz

1

Finally, using the relationship between temperature and entropy we arrive at the desired conclusion: zi . Once again, in the case of periodic boundary conditions this proof only applies to components of the momenta. The reason is that the domain associated with a component of the coordinates is typically strictly contained within the energy shell, hence H (z ) is not equal to E on the boundary of the domain of integration. However, for the components of the momenta (which are unbounded), the inclusion is reversed, and we reach the energy shell before reaching the edge of the domain (since the domain of the momenta is the entire real line). Hence, a dierent proof is required if we want to show the Virial Theorem is true for the coordinates under periodic boundary conditions. 4 H = ij kB T, zj

In this section we consider an alternative approach for proving the Virial Theorem, using the Equipartition Theorem with the Clausius Virial Theorem. Theorem (Equipartition): Given a system governed by the canonical or microcanonical ensemble, and a component of phase-space, zi , which appears quadratically in the energy function, and is dened on the entire real line, then H zi = kB T zi Proof: Clearly the energy is unbounded as zi approaches the boundary of its domain (innity), hence both Lemmas 1 and 2 apply, . Note that for classical mechanical systems, components of the momenta always satisfy the assumptions of the Equipartition Theorem. Theorem (Classical Clausius): Given a system governed by the microcanonical ensemble, with a bounded and dierentiable trajectory in phase space, then pi H H = qi . pi qi

Proof: Using Hamiltons equations of motion, we have the following identity: d H H (qi pi ) = pi q i + qi p i = pi qi dt pi qi Hence we need only to prove that d (qi pi ) /dt is zero. By the ergodic hypothesis, the ensemble average is the same as the time average. Using the time average, we have d 1 (qi pi ) := lim dt

0

Since both the coordinates and momenta are bounded for all time, the expression must be zero. Hence, pi . Note that given Lemma 2, the Classical Clausius theorem does not provide any new information. In particular, it cannot be applied in this form to systems with periodic boundary conditions for one of two possible reasons. Suppose we enforce the coordinate path to remain within the unit periodic cell, translating each coordinate when it reaches the edge of the cell. In this case the trajectory is clearly not globally dierentiable, with discontinuities at each point that the trajectory reaches the edge of the cell. On the other hand, we could take the view that the coordinate path can wander freely in space, without boundaries, and compute forces based on the minimum (or multiple) image convention. Now we have the problem that the trajectory is not uniformly 5 H H , = qi pi qi

bounded, and hence the Classical Clausius theorem still does not apply. For the remainder of this section, we will adopt the convention of an unbounded, but dierentiable coordinate path, and introduce a Modied Clausius theorem. Theorem (Modied Clausius): Given a system governed by the microcanonical ensemble, with unbounded coordinates, the Hamiltonian invariant under periodic translation, globally bounded momenta, and a dierentiable a trajectory in phase space, then pi H H 1 q i = Li lim t t pi qi |pi (k )| .

k

Here, Li is the length of the simulation cell in the direction of the coordinate qi . The index k is over all crossings of a cell boundary with time of each crossing given by k . The variable q i is the periodic version of qi , where q i is contained inside of a single unit cell. Proof: We start by decomposing qi into a bounded periodic component, q i , and a sum of step-functions, qi . We dene the later term as follows: qi (t) := qi (t) q i (t) =

k

Li k (t k ) .

The summation is over all crossings of a periodic cell, with Li and k dened as in the assumptions of the Theorem. The symbol k represents the sign of the crossing, depending on if it crosses the left or right d boundary of the cell. Expanding the expression for dt (pi qi ) as before results in d d d (pi q i ) + (pi qi ) = (pi qi ) = pi q i + qi p i , dt dt dt or after subtracting qi p i from both sides d d (pi q i ) + (pi qi ) qi p i = pi q i + q i p i . dt dt For the rst term we can use the fact that q i and pi are bounded to conclude that d 1 ( qi pi ) := lim dt

0

Applying the denition of q , we can expand the left-hand side to obtain d qi dt 1 lim

pi

:= =

pi (t) Li

0 k

k (t k ) dt,

lim

1 Li

k pi (k ) .

k

Figure 1: Example of a decomposition of an unbounded qi into the sum of a periodic, q i , part and a series of step functions, qi . If we recognize that k and pi (k ) always have the same sign (i.e. the crossing direction and the direction of the momenta are always the same), we can replace k pi (k ) with the absolute value of the momenta, yielding in the desired result: 1 H H lim Li |pi (k )| = pi q i , pi qi

k

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