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Static Resources St Crib

Static Resources St Crib

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Published by: Emily Huang on Apr 28, 2012
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Statistical Thermodynamics Crib Sheet

The Molecular Partition Function The molecular partition function, q, can be thought of as a measure of the average number of thermally accessible states available to a system at a given temperature, at equilibrium. It can be defined as a sum over states, j with energies j : q=


j /kB T

or as a sum over energy levels, i, where each level has degeneracy gi (i.e. there are gi states with energy i ): q=

g i e−

i /kB T

The energies in these expressions are measured relative to the ground-state, so that 0 = 0. It is usually a good approximation to factorise the partition function in terms of the various modes of molecular motion: q = qtrans qrot qvib qelec The Translational Molecular Partition Function For translational motion of a molecule with total mass m inside a one-dimensional box of length Lx , the energy levels are: Enx = h2 n2 x , 8mL2 x nx = 1, 2, 3, . . .

Factorising the total translational partition functions: qtrans = qx qy qz , and approximating the summation for each dimension as an integral gives: qtrans = V Λ3 h where Λ = √ 2πmkB T

for a box of volume V = Lx Ly Lz . Λ is called the thermal wavelength. The Rotational Molecular Partition Function For a diatomic molecule treated as a rigid rotor, the energy levels are: EJ = hcBJ(J + 1) with gJ = 2J + 1, where B = h cm−1 8π 2 Ic

and J = 0, 1, 2, . . . is the rotational quantum number. In the high-temperature limit, where the summation over J can be replaced by an integration: qrot = T σθrot where θrot = hcB kB

so that there is a fixed temperature. there are energy levels given by: 1 Ev = hc˜(v + 2 ). qelec can be treated as a two level system: qelec = g0 + g1 e− The Canonical Partition Function A system of N particles within a fixed volume V can be imagined to be replicated ˜ ˜ N times (where N can be very large. These N systems constitute the canonical ensemble. and 2 for homonuclear diatomics. where the rotational temperature θrot is comparable to or greater than T . where each qvib. kB T kB T This can be evaluated analytically using the formula S∞ = a/(1 − r).. and qvib ≈ 1. . and is unrelated to N ).˜1 qvib.˜k is an infinite geometric progresν ν ν ν sion: relative to the v = 0 level. though: for example. The number of systems within the ensemble with energy Ei is ni . distributed according to: ˜ ni ˜ e−Ei /kB T = ˜ Q N where Q = i 1 /kB T e−Ei /kB T . At low temperatures (and for H2 even at room temperature). equal to 1 for heteronuclear diatomics. qvib = 1 1 − exp(−θvib /T ) where θvib = hc˜ ν kB T . the summation must be performed numerically.σ is the symmetry number. For a diatomic molecule (and for each normal mode of a polyatomic molecule). with each (closed) system in thermal contact with the others. the NO molecule has a doubly-degenerate ground state (g0 = 2) and a low-lying doubly-degenerate excited state ( 1 = 121 cm−1 . . At room temperature. (taking into account any nuclear spin effects explicitly): hcBJ(J + 1) (2J + 1) exp − qrot = kB T J The Vibrational Molecular Partition Function For each normal mode of a molecule (in the simple harmonic approximation). qvib.˜3 .˜2 qvib.˜k = 1 + exp − ν 2hc˜k ν hc˜k ν + exp − + . There are some notable exceptions. ˜ T .. ν where ν = ˜ 1 2πc k cm−1 µ The vibrational partition function can be factorised into each normal mode: qvib = qvib. for most diatomic molecules θvib The Electronic Molecular Partition Function The excited electronic states of most molecules are so much higher in energy than the ground electronic state (relative to kB T ) that the approximation qelec = g0 is usually a good one. g1 = 2).

known as the Massieu bridge): A = A(0) − kB T ln Q From this equation. there is a simple relationship between Q and q: Q = qN for distinguishable particles Q = q N /N ! for indistinguishable particles Identical but distinguishable particles (such as those in a crystal lattice. there is no way of telling between different particles in the same state. qN = q N . . so this product over-counts the number of states by a factor of N !.˜ Q is the canonical partition function.T .they may interact with each other. expressions for many other thermodynamic functions can be obtained. Q is entirely general. y. S=− ∂A ∂T V . the residual entropy at 0 K) is given by: U − U (0) + kB ln Q S= T An important use of this formula is in calculating the entropy of n moles of an ideal gas (for which only translational motion contributes) . For indistinguishable particles (such as those of an ideal gas). . in terms of q: U = U (0) + N kB T 2 ∂ ln q ∂T V The entropy of the system (relative to S(0). z) co-ordinates) have Q = q1 q2 q3 . When the particles are taken to be non-interacting.the result is the Sackur-Tetrode equation: S = nR ln e5/2 V nNA Λ3 The Helmholtz Free energy has a simple relationship to Q. For example. p=− ∂A ∂V T . The Stirling approximation is useful in manipulating equations involving N !: ln N ! ≈ N ln N − N Some Thermodynamic Formulae The internal energy of a system is U = U (0) + kB T 2 ∂ ln Q ∂T for large N V where U (0) is its value at T = 0 K (this information is not contained in the partition function). For non-interacting particles. and does not rely on the particles being independent . µ= ∂A ∂n V. which can be referred to by their (x. for large N this distribution is overwhelmingy the most likely and defines the properties of the system.

A full set of relations for systems of constant composition. . etc. y): df = is exact if ∂f ∂x dx + ∂f ∂y dy y x ∂2f ∂ 2f = ∂y∂x ∂x∂y dU . H. and A are state functions. . G = A + pV the Gibb’s free energy.. undergoing reversible change with no non-expansion work is given below: dU = dq + dw H = U + pV G = H − TS A = U − TS ⇒ dU = T dS − pdV ⇒ dH = T dS + V dp ⇒ dG = V dp − SdT ⇒ dA = −pdV − SdT T = T = V = p=− ∂U ∂S ∂H ∂S ∂G ∂p ∂A ∂V .. . G. Therefore. because U . p=− V = ∂U ∂V ∂H ∂p V S p S T S=− S=− ∂G ∂T ∂A ∂T p T V The Maxwell Equations A differential df of a function f (x. ∂2U ∂V ∂S = ∂2U ∂S∂V ⇒ ∂T ∂V =− ∂p ∂S S V The other three Maxwell equations are derived in a similar way: ∂T ∂p ∂V ∂T ∂p ∂T = = = ∂V ∂S p ∂S − ∂p T ∂S ∂V T S p V .From these. U = A + T S gives the internal energy. dG. and dA above are exact differentials. dH.

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