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Section 2.4: Probability Calculations • To calculate the probability of finding a system in a given state, we use The Fundamental Postulate of Statistical Mechanics: “An isolated system in equilibrium is equally likely to be found in any one of it’s accessible states.” • There will always be an uncertainty in our knowledge of the system energy ≡ δE. Suppose that we know that the energy of the system is in the range E to E + δE. The Fundamental Postulate: “An isolated system in equilibrium is equally likely to be found in any one of it’s accessible states.” • There is always an uncertainty in our knowledge of the system energy ≡ δE. Suppose that we know that the energy of the system is in the range E to E + δE. • Define: Ω(E) ≡ Total number of accessible states in this range. y ≡ A macroscopic system parameter (pressure, magnetic moment, etc.). • Define: Ω(E;yk) ≡ A subset of Ω(E) for which y ≡ yk (yk = A particular value of y) • Let P(y = yk) ≡ probability that y ≡ yk. By the Fundamental Postulate of Statistical Mechanics this is: Pk P(y = yk) ≡ [Ω(E;yk)]/[Ω(E)] • Now, calculate the mean (expected) value of y: • From probability theory, this is simply: <y> ≡ ∑kykPk ∑kyk[Ω(E;yk)]/[Ω(E)] • Clearly, to calculate this, we need to know both Ω(E) & Ω(E;yk). This will be discussed in detail as we go through this chapter! • In principle (if we know the Ω’s) this calculation is easy. • Example: Take 3 particles of spin ½ in an external magnetic field again. • Suppose that we know from measurement that the total energy is E = - μH. As we’ve seen, there are only 3 accessible states for E = - μH. These are: (+,+,-) (+,-,+) (-,+,+). Question: • Probability of finding spin #1 in the “up” position? • To answer, we need Ω(E) for this problem. We had: Ω(E) ≡ Ω(E = -μH) ≡ 3 and Ω(E;yk) ≡ Ω(E = -μH; spin 1 is “up”) ≡ 2 • For total the energy E = - μH, the 3 accessible states are: (+,+,-) (+,-,+) (-,+,+). • Probability of finding spin #1 in “up” position? Formally: P(E; y = yk) ≡ [Ω(E;yk)/Ω(E)] or P(E = -μH; spin 1 is “up”) ≡ [Ω(E = -μH; spin 1 is “up”)/Ω(E = -μH)] We just saw that Ω(E) ≡ Ω(E = -μH) ≡ 3 & Ω(E;yk) ≡ Ω (E = -μH; spin 1 is “up”) ≡ 2 • So, The Probability that spin #1 is “up” is: P(spin 1 “up”) ≡ (⅔) • The Probability that spin #1 is “down” is: P(spin 1 “down”) ≡ (⅓) • Since we have the probability, P(E; y = yk) we can use it to find answers to problems like: • Calculate the Mean (average) Magnetic Moment of Spin # 1. <μz> ≡ ∑kμzkP(μz= μzk) (Sum goes over k = “up” & k = “down”) <μz> = P(#1 “up”)(μ) + P(#1 “down”)(-μ) = (⅔)(μ) + (⅓)(-μ) so <μz> = (⅓)μ Section 2.5: Energy Dependence of the Density of States Note! This section is one of the most important sections in the chapter!! • We’ve just seen that the probability that parameter y has a value yk is: P(y = yk) ≡ [Ω(E;yk)/Ω(E)] Ω(E) ≡ # accessible states with energy between E & E + δE. To do probability calculations, we obviously need to know the E dependence of Ω (E). A goal of the following discussion is to find an approximation to the E dependence of Ω(E). P(y = yk) ≡ [Ω(E;yk)/Ω(E)] GOAL: Find an Approximation for the E dependence of Ω(E). • No rigorous math! Physical arguments & “hand waving.” Consider a Macroscopic System with f degrees of freedom. f is huge! f ~ 1024. • Energy is in range E to E + δE. Of course, Ω(E) δE. Extrapolating earlier discussion of the 1d oscillator: Ω(E) ~ Phase space volume in this energy range. • Define Ω(E) ≡ ω(E)δE. ω(E) ≡ Density of states Goal: Estimate the E dependence of Ω(E) (or ω(E)). So, ~ how many accessible states are there for a macroscopic system (f ~ 1024) at energy E? • Not interested in exact results. We want an order of magnitude estimate!! The result is abstract, but very significant!! Let Φ(E) ≡ Total # of quantum states for all energies E´ ≤ E. Φ(E) ≡ Total # of quantum states for all energies E´ ≤ E. • Consider 1 “typical” degree of freedom. ε ≡ energy associated with that degree of freedom. Let φ(ε) ≡ total # of quantum states for this degree of freedom. • Generally, φ(ε) increases with increasing ε. So, we can write: φ(ε) εα (α ~ 1) (1) φ(ε) ε (1) • For the system, replace the energy E by an “average energy” for a system of f degrees of freedom: ε (E/f) (2) f degrees of freedom & φ(ε) states associated with each. Total # of states associated with f degrees of freedom ≡ product of # associated with each: Φ(E) [φ(ε)]f (3) Now, use (1), (2), & (3) together: • So, we have: φ(ε) ε (1), and ε (E/f) (2) Φ(E) [φ(ε)]f (3) • Using (1), (2), & (3) together: The total # of states for all energies E´ ≤ E is roughly: Φ(E) [φ(ε)]f So Φ(E) [E/f]f or Φ(E) Ef or So finally: Φ(E) ≡ AEf (4) A = constant Ω(E) ≡ # accessible states with energy between E & E + δE • So, we can write: Ω(E) ≡ Φ(E + δE) - Φ(E); δE <<< E Expand Φ in a Taylor’s series & keep only the lowest order term: Ω(E) (Φ/E)δE [(Ef)/E]δE Ω(E) Ef-1δE Ef δE (f >> 1) Ω(E) Ef δE (f ~ 1024) Ω(E) is an incomprehensibly Rapidly Increasing Function of E!! •Briefly look at some numbers with powers of 10 in the exponent to get a “feel” for the “bigness” of Ω(E) Ef : •Briefly look at some numbers with powers of 10 in the exponent to get a “feel” for the “bigness” of Ω(E) Ef : 1. Approximate age of the Universe in seconds = “only” 1018 s! This is a 1 with 18 zeros after it! •Briefly look at some numbers with powers of 10 in the exponent to get a “feel” for the “bigness” of Ω(E) Ef : 1. Approximate age of the Universe in seconds = “only” 1018 s! This is a 1 with 18 zeros after it! 2. Universe volume divided by the volume of a grain of sand = “only” 1090! This is a 1 with 90 zeros after it! Ω(E) f E δE, Consider f ~ 24 10 : • By what factor does Ω (E) change when E changes by only 1%? Let r ≡ [Ω (E + 0.01E)/Ω (E)] = • Evaluate r using logarithms: f (1.01) log10(r) = 1024log10(1.01) 4.32 1021 So, r 10x, where x 4.32 1021, or r ~ 1 with 4.32 1021 zeros after it! Ω(E) f E δE, Consider f ~ 24 10 : • Consider the same problem again, but let E increase by only 10-6E. By what factor does Ω (E) change? Let r ≡ [Ω (E + 10-6E)/Ω (E)] = (1.0 +10-6)f •Evaluate r using logarithms: log10(r) = 1024log10(1.0 +10-6) 4.34 1017, So r 10y, where y = 4.34 1017, or r ~ 1 with 4.34 1017 zeros after it! • Finally, consider 2 seemingly similar numbers: u 10 , and 24 10 C= u= v 24 D = 10 , v = 2 10 • Are these similar numbers?? • Finally, consider 2 seemingly similar numbers: u 10 , and 24 10 C= u= v 24 D = 10 , v = 2 10 • Are these similar numbers?? NO!!! Their ratio is: (D/C) = 10u • Finally, consider 2 seemingly similar numbers: u 10 , and 24 10 C= u= v 24 D = 10 , v = 2 10 • Are these similar numbers?? NO!!! Their ratio is: (D/C) = 10u That is, D is 10u times (u = 1024!) larger than C u = 1 with 24 10 zeros after it! • The bottom line is that: Ω(E) is • The bottom line is that: Ω(E) is An Almost Incomprehensibly • The bottom line is that: Ω(E) is An Almost Incomprehensibly Enormously Rapidly Varying • The bottom line is that: Ω(E) is An Almost Incomprehensibly Enormously Rapidly Varying Function of E (!!) Simple Special Case: Ideal, Monatomic Gas • To make this general discussion clearer, as an example, lets consider a classical ideal, monatomic gas, with N identical molecules confined to volume V. • Lets calculate Ω(E) exactly for this case. Ideal Gas NO INTERACTION between molecules. ~ Valid approximation for real gases in the low density limit. • Classical ideal, monatomic gas, N identical molecules in volume V. Calculate Ω(E) for this case. Ideal Gas No Interaction between molecules. • In this case, the total energy E of the gas is the sum of the kinetic energies of the N molecules, each of mass m: E (2m)-1∑(i = 1,N)(pi)2, pi = 3d momentum of particle i. • Ω(E) ≡ # of accessible states in the interval E to E + δE • Ω(E) ≡ # of cells in phase space between E & E + δE. • Ω(E) volume of phase space between E & E + δE. • In what follows, recall the 1d oscillator where Ω(E) = area between 2 ellipses. • Ω(E) volume of phase space between E & E + δE. 2mE = ∑ (i = 1,N) ∑ (α = x,y,z) (piα)2 • The energy is independent of the particle positions! piα = α component of momentum of particle i. Ω(E) ∫ (E E + δE) d3r1d3r2…d3rNd3p1d3p2…d3pN A 6N dimensional volume integral! • The limits E & E + δE are independent of the ri’s The position integrals for each ri can be done immediately: ∫d3ri ≡ V ∫d3r1d3r2…d3rN ≡ VN Ω(E) VN ∫ d3p1d3p2…d3pN (E E + δE) Ω(E) VN ∫(E E + δE) d3p1d3p2…d3pN (1) A 3N dimensional volume integral in p space • Consider the sum 2mE = ∑(i = 1,N)∑(α = x,y,z) (piα)2 (2) (2) ≡ “sphere” in 3N dimensional momentum space. • Briefly consider the case of 1 particle only. (2) is: 2mE = (px)2 + (py)2 + (pz)2 This is a “sphere” in momentum space of “radius” R(E) = (2mE)½ • For 1 particle, the 3d “sphere volume” [R(E)]3 (E)(3/2) • For N particles in 3N dimensional momentum space, (2) ≡ a “sphere” of “radius” R(E) = (2mE)½ So, the 3N dimensional “sphere volume” is [R(E)]3N (E)(3N/2) • Lets write: Ω(E) VNG(E) where: G(E) ≡ ∫(E E + δE) d3p1d3p2…d3pN (3) • G(E) ≡ Volume of “spherical shell” between E & E + δE This is shown schematically for 2 dimensions in the figure: • G(E) [R(E)]3N (E)(3N/2) Ω(E) VN(E)(3N/2) • Write: Ω(E) = BVN(E)(3N/2) • B = constant, Ω(E) = # of accessible states for an ideal gas in the energy interval E to E + δE • In summary, for the Ideal Gas, we found: Ω(E) = BVN(E)(3N/2)δE = # accessible states of an ideal gas in the energy interval E to E + δE, B = constant • In general, we found for f degrees of freedom, Ω(E) = AEf δE, A = constant • For the ideal gas, f = 3N, so we got an E dependence of E(½)f instead of Ef, but, again, all of this was Approximate & Order of Magnitude. • So, no worries about the difference between f & (½)f.