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Microcanonical Ensemble ME346A Introduction to Statistical Mechanics { Wei Cai { Stanford University { Win 2011 Handout 5. Microcanonical Ensemble January 19, 2011 Contents 1 Properties of flow in phase space 2 1.1 Trajectories in phase space . .2 1.2 One trajectory over long time . .3 1.3 An ensemble of points flowing in phase space . .6 2 Microcanonical Ensemble 7 2.1 Uniform density assumption . .7 2.2 Ideal Gas . .9 2.3 Entropy . 13 1 The purpose of this lecture is 1. To justify the \uniform" probability assumption in the microcanonical ensemble. 2. To derive the momentum distribution of one particle in an ideal gas (in a container). 3. To obtain the entropy expression in microcanonical ensemble, using ideal gas as an example. Reading Assignment: Sethna x 3.1, x 3.2. 1 Properties of flow in phase space 1.1 Trajectories in phase space Q: What can we say about the trajectories in phase space based on classical mechanics? A: 1. Flow line (trajectory) is completely deterministic @H q_i = @pi @H (1) p_i = − @qi Hence two trajectories never cross in phase space. This should never happen, otherwise the flow direction of point P is not determined. 2. Liouville's theorem dρ @ρ ≡ + fρ, Hg = 0 (2) dt @t So there are no attractors in phase space. 2 This should never happen, otherwise dρ/dt > 0. Attractor is the place where many trajectories will converge to. The local density will increase as a set of trajectories converge to an attractor. 3. Consider a little \cube" in phase space. (You can imagine many copies of the system with very similar initial conditions. The cube is formed all the points representing the initial conditions in phase space.) Let the initial density of the points in the cube be uniformly distributed. This can be represented by a density field ρ(µ; t = 0) that is uniform inside the cube and zero outside. As every point inside the cube flows to a different location at a later time, the cube is transformed to a different shape at a different location. Due to Liouville's theorem, the density ρ remain ρ = c (the same constant) inside the new shape and ρ = 0 outside. Hence the volume of the new shape remains constant (V0). 1.2 One trajectory over long time Q: Can a trajectory from on point µ1 in phase space always reach any other point µ2, given sufficiently long time? A: We can imagine the following possibilities: 3 1. We know that the Hamiltonian H (total energy) is conserved along a trajectory. So, there is no hope for a trajectory to link µ1 and µ2 if H(µ1) 6= H(µ2). Hence, in the following discussion we will assume H(µ1) = H(µ2), i.e. µ1 and µ2 lie on the same constant energy surface: H(µ) = E. This is a (6N − 1)-dimensional hyper-surface in the 6N-dimensional phase space. 2. The trajectory may form a loop. Then the trajectory will never reach µ2 if µ2 is not in the loop. 3. The constant energy surface may break into several disjoint regions. If µ1 and µ2 are in different regions, a trajectory originated from µ1 will never reach µ2. Example: pendulum 4. Suppose the trajectory does not form a loop and the constant energy surface is one continuous surface. The constant energy surface may still separate into regions where trajectories originated from one region never visit the other region. | This type of system is called non-ergodic. 4 5. If none of the above (1-4) is happening, the system is called Ergodic. In an ergodic system, we still cannot guarantee that a trajectory starting from µ1 will exactly go through any other part µ2 in phase space. (This is because the dimension of the phase space is so high, hence there are too many points in the phase space. One trajectory, no matter how long, is a one-dimensional object, and can \get lost" in the phase space, i.e. not \dense enough" to sample all points in the phase space.) But the trajectory can get arbitrarily close to µ2. \At time t1, the trajectory can pass by the neighborhood of µ2. At a later time t2, the trajectory passes by µ2 at an even smaller distance..." After a sufficiently long time, a single trajectory will visit the neighborhood of every point in the constant energy surface. | This is the property of an ergodic system. Ergodicity is ultimately an assumption, because mathematically it is very difficult to prove that a given system (specified by its Hamiltonian) is ergodic. 5 1.3 An ensemble of points flowing in phase space Now imagine a small cube (page 1) contained between two constant-energy surfaces H = E, H = E + ∆E. As all points in the cube flows in phase space. The cube transforms into a different shape but its volume remains V0. The trajectories of many non-linear systems with many degrees of free- dom is chaotic, i.e. two trajecto- ries with very similar initial con- ditions will diverge exponentially with time. Q. How can the volume V0 remain constant while all points in the orig- inal cube will have to be very far apart from each other as time in- creases? A: The shape of V0 will become very complex, e.g. it may consists of many thin fibers distributed almost every where between the two con- stant energy surface. At a very late time t, ρ(µ; t) still has the form of C µ 2 V ρ(µ; t) = 0 (3) 0 µ 2= V0 except that the shape of V0 is dis- tributed almost every where be- tween constant energy surface. 6 A density function ρ(µ; t) corresponds to an ensemble of points in phase space. Suppose we have a function A(µ) defined in phase space. (In the pendulum example, we have considered A = θ2.) The average of function A(µ) over all points in the ensemble is called the ensemble average. If ρ changes with time, then the ensemble average is time dependent Z hAi(t) ≡ d6N µ A(µ) ρ(µ; t) (4) From experience, we know that many system will reach an equilibrium state if left alone for a long time. Hence we expect the following limit to exist: lim hAi(t) = hAieq (5) t!1 hAieq is the \equilibrium" ensemble average. Q: Does this mean that lim ρ(µ; t) = ρeq(µ)? (6) t!1 No. In previous example, no matter how large t is, C µ 2 V ρ(µ; t) = 0 (7) 0 µ 2= V0 The only thing that changes with t is the shape of V0. The shape continues to transform with time, becoming thinner and thinner but visiting the neighborhood of more and more points in phase space. So, lim ρ(µ; t) DOES NOT EXIST! t!1 What's going on? 2 Microcanonical Ensemble 2.1 Uniform density assumption In Statistical Mechanics, an ensemble (microcanonical ensemble, canonical ensemble, grand canonical ensemble, ...) usually refers to an equilibrium density distribution ρeq(µ) that does not change with time. The macroscopically measurable quantities is assumed to be an ensemble average over ρeq(µ). Z 6N hAieq ≡ d µ A(µ) ρeq(µ) (8) 7 In the microcanonical ensemble, we assume ρeq to be uniform inside the entire region between the two constant energy surfaces, i.e. C0 E ≤ H(µ) ≤ E + ∆E ρ (µ) = ρ (µ) = (9) eq mc 0 otherwise There is nothing \micro" in the microcanonical ensemble. It's just a name with an obscure historical origin. Q: How do we justify the validity of the microcanonical ensemble assumption, given that lim ρ(µ; t) 6= ρmc(µ) (recall previous section)? t!1 A: 1. As t increases, ρ(µ; t) becomes a highly oscillatory function changing volume rapidly between C and 0, depending on whether µ is inside volume V0 or not. But if function A(µ) is smooth function, as is usually the case, then it is reasonable to expect Z Z 6N 6N lim d µ A(µ) ρ(µ; t) = d µ A(µ) ρmc(µ) (10) t!1 In other words, lim ρ(µ; t) and ρeq(µ) give the same ensemble averages. t!1 2. A reasonable assumption for ρeq(µ) must be time stationary, i.e. @ρ eq = −{ρ ;Hg = 0 (11) @t eq Notice that 0 ρmc(µ) = [Θ(H(µ) − E) − Θ(H(µ) − E − ∆E)] · C (12) where Θ(x) is the step function. 8 Because ρmc is a function of H ) fρmc;Hg = 0. Hence @ρ mc = 0 (13) @t The microcanonical ensemble distribution ρmc is stationary!. 3. The microcanonical ensemble assumption is consistent with the subjective probability assignment. If all we know about the system is that its total energy H (which should be conserved) is somewhere between E and E + ∆E, then we would like to assign equal probability to all microscopic microstate µ that is consistent with the constraint E ≤ H(µ) ≤ E + ∆E. 2.2 Ideal Gas Ideal gas is an important model in statis- tical mechanics and thermodynamics. It refers to N molecules in a container. The interaction between the particles is suffi- ciently weak so that it will be ignored in many calculations. But conceptually, the interaction cannot be exactly zero, other- wise the system would no longer be ergodic | a particle would never be able to trans- fer energy to another particle and to reach equilibrium when there were no interac- tions at all. Consider an ensemble of gas contain- ers containing ideal gas particles (mono- atomic molecules) that can be described by the microcanonical ensemble.
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