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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

e−

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 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

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. At low temperatures (and for H2 even at room temperature). the summation must be performed numerically.. and 2 for homonuclear diatomics. so that there is a ﬁxed temperature. At room temperature. . though: for example. there are energy levels given by: 1 Ev = hc˜(v + 2 ).˜1 qvib. qvib.σ is the symmetry number. qvib = 1 1 − exp(−θvib /T ) where θvib = hc˜ ν kB T .˜k is an inﬁnite geometric progresν ν ν ν sion: relative to the v = 0 level.˜3 .˜k = 1 + exp − ν 2hc˜k ν hc˜k ν + exp − + . where the rotational temperature θrot is comparable to or greater than T . distributed according to: ˜ ni ˜ e−Ei /kB T = ˜ Q N where Q = i 1 /kB T e−Ei /kB T . (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). There are some notable exceptions. .˜2 qvib. For a diatomic molecule (and for each normal mode of a polyatomic molecule). where each qvib. and is unrelated to N ). with each (closed) system in thermal contact with the others. These N systems constitute the canonical ensemble. kB T kB T This can be evaluated analytically using the formula S∞ = a/(1 − r). the NO molecule has a doubly-degenerate ground state (g0 = 2) and a low-lying doubly-degenerate excited state ( 1 = 121 cm−1 . g1 = 2). ˜ T . The number of systems within the ensemble with energy Ei is ni . ν where ν = ˜ 1 2πc k cm−1 µ The vibrational partition function can be factorised into each normal mode: qvib = qvib.. equal to 1 for heteronuclear diatomics. and qvib ≈ 1. 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.

Q is entirely general. For example. y. in terms of q: U = U (0) + N kB T 2 ∂ ln q ∂T V The entropy of the system (relative to S(0). . for large N this distribution is overwhelmingy the most likely and deﬁnes the properties of the system.T .˜ Q is the canonical partition function. S=− ∂A ∂T V . there is no way of telling between diﬀerent particles in the same state. p=− ∂A ∂V T . For indistinguishable particles (such as those of an ideal gas). 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). µ= ∂A ∂n V. so this product over-counts the number of states by a factor of N !. 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. known as the Massieu bridge): A = A(0) − kB T ln Q From this equation. 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) . When the particles are taken to be non-interacting. z) co-ordinates) have Q = q1 q2 q3 .they may interact with each other.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. and does not rely on the particles being independent . . qN = q N . which can be referred to by their (x. For non-interacting particles. expressions for many other thermodynamic functions can be obtained.

G. and dA above are exact diﬀerentials.. U = A + T S gives the internal 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 . . A full set of relations for systems of constant composition. Therefore. and A are state functions. H. dG.From these. ∂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 . 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. dH. . G = A + pV the Gibb’s free energy.. etc. . because U . y): df = is exact if ∂f ∂x dx + ∂f ∂y dy y x ∂2f ∂ 2f = ∂y∂x ∂x∂y dU .

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