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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 dened as a sum over states, j with energies j : q=
j

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=
i

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 3 h where = 2mkB T

for a box of volume V = Lx Ly Lz . 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 cm1 8 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 rot where rot = hcB kB

is the symmetry number, equal to 1 for heteronuclear diatomics, and 2 for homonuclear diatomics. At low temperatures (and for H2 even at room temperature), where the rotational temperature rot is comparable to or greater than T , the summation must be performed numerically, (taking into account any nuclear spin eects 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), there are energy levels given by:
1 Ev = hc(v + 2 ),

where =

1 2c

k cm1

The vibrational partition function can be factorised into each normal mode: qvib = qvib,1 qvib,2 qvib,3 . . . where each qvib,k is an innite geometric progres sion: relative to the v = 0 level, qvib,k = 1 + exp 2hck hck + exp + ... kB T kB T

This can be evaluated analytically using the formula S = a/(1 r). For a diatomic molecule (and for each normal mode of a polyatomic molecule), qvib = 1 1 exp(vib /T ) where vib = hc kB T , and qvib 1.

At room temperature, for most diatomic molecules vib 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. There are some notable exceptions, though: for example, the NO molecule has a doubly-degenerate ground state (g0 = 2) and a low-lying doubly-degenerate excited state ( 1 = 121 cm1 , g1 = 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 xed volume V can be imagined to be replicated N times (where N can be very large, and is unrelated to N ), with each (closed) system in thermal contact with the others, so that there is a xed temperature, T . These N systems constitute the canonical ensemble. The number of systems within the ensemble with energy Ei is ni , distributed according to: ni eEi /kB T = Q N where Q =
i
1 /kB T

eEi /kB T

Q is the canonical partition function; for large N this distribution is overwhelmingy the most likely and denes the properties of the system. Q is entirely general, and does not rely on the particles being independent - they may interact with each other. When the particles are taken to be non-interacting, 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, which can be referred to by their (x, y, z) co-ordinates) have Q = q1 q2 q3 . . . qN = q N . For indistinguishable particles (such as those of an ideal gas), there is no way of telling between dierent particles in the same state, so this product over-counts the number of states by a factor of N !. 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

where U (0) is its value at T = 0 K (this information is not contained in the partition function). For non-interacting particles, in terms of q: U = U (0) + N kB T 2 ln q T

The entropy of the system (relative to S(0), 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) - the result is the Sackur-Tetrode equation: S = nR ln e5/2 V nNA 3

The Helmholtz Free energy has a simple relationship to Q, known as the Massieu bridge): A = A(0) kB T ln Q From this equation, expressions for many other thermodynamic functions can be obtained. For example, S= A T
V

p=

A V

A n

V,T

From these, U = A + T S gives the internal energy, G = A + pV the Gibbs free energy, etc... A full set of relations for systems of constant composition, 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 , , , , p= V = U V H p

S= S=

G T A T

The Maxwell Equations A dierential df of a function f (x, y): df = is exact if f x dx + f y dy

2f 2f = yx xy

dU , dH, dG, and dA above are exact dierentials, because U , H, G, and A are state functions. Therefore, 2U V S = 2U SV T V = p S

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

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