Apr. 15 Mayer Cluster Expansion ‘The grand canonical ensemble gives us a powerful tool to discuss the propertis of gases in the case that they are not ideal. In this lecture, I will derive an elegant method for computing the properties of a gas of interacting molecules in an expansion in the density. For an ideal gas, NT Pr vy ? nT where n is the particle density If the gas is made of molecules that interact with one another, but the ges is very dilute, the interactions occur very rarely, and so the ideal gas relations apply. As the density is increased, the pressure should deviate from the ideal gas formula, becoming higher for repulsive interactions and lower for attractive interactions. The general expression for the pressure as a function of n and T is called the equation of state. This argument motivates that we can expand the equation of state of a gas about the low density limit pe at CA + 2 BO) + POM +4.) The coefficients B(T), C(T), and so on, are called the virial coefficients. At high densities, the equation of state deviates essentially from the ideal gas form, in a way that implies the presence of a liquid phase and a phase transition between liquid and gas states. We will discuss this later in the course. 1Here, I will investigate how to compute the coefficients of the virial expansion in a systematic way. ‘The grand canonical ensemble and the chemical potential provide useful tools for this study. In the grand canonical ensemble, we do not need to fix the particle mmber, and so we can use as many particles as we want. in describing an interaction of many particles. The cost for introducing an additional particle is the factor e%. At the end of the analysis, we will use the equation & ap lay 7 7 N to eliminate pin terms of N or n = N/V. Using this strategy, I will now work out the grand canonical partition function for interacting atoms in a fairly explicit way. For simplicity, I will assume that the atoms are spherical and interact through a pairwise potential V(|%1 — Za|). A typical form for an interatomic potential is Veo ‘The long-range part of this potential is an attractive van der Waals potential, of the form Vie ~ “he ‘The short-range part of the potential provides a repulsive core. You will often see this potential written more explicitly as the Lennard-Jones potential - A_SB Vey os =(‘The exponent 12 has no significance; it was originally introduced to as a convenience to minimize the computer time needed to compute this potential repeatedly.) ‘The attractive and repulsive parts of this potential compete, and the competition is a function of temperature. ‘The potential is singular as r — 0, but I will structure the expansion so that it involves the nonsingular function — @Vir) a? With this interaction w oo 2 3 -G2 Pe = L GON, (dade crs = = te ar isi tm 2 MN i> Geko The notation (ij) is read: pairs i,j, or 1S i 2, the sum over NV can be written as ~GVORAK)or me eM Litas (AM «. There is an overall factor of exp[éV], the zeroth-order partition function. Note that ‘the integral over dx is finite, since e~°'™) is bounded as ¢ > 0 and - evs) aM 44 OCR) & Woe ‘The correction will give a term of order n? in & that will contribute to the first virial coefficient B(T). In principle, we could go ahead right now to compute B(7), but itis interesting to first go on to analyze contributions to = of higher power in the density. So, consider next the term with two factors of (e~” — 1). ‘There are two types of terms, those that share a particle, and those that do not. In the terms that share a particle, called the shared particle i and the other two particles j,k. The number of sueh terms is NON-NCN-D)in which the factor } accounts the fact that it does not matter which particle we call j and which we call k. The contribution from these terms is A sX NIN NB S we sl Uv VOR) Goa dy dy ™ [e 3° » As above, set W ~ (iV — 3), Then this expression is © sos WED Ve SB Fev. igy. Se Rye Neo Ve 2 oY sey Gd NEMA] Again, a factor of the zeroth-order partition fimction appears in front. The correction term is proportional to €°V. “fe oti J ‘The terms with no particles in common have a different structure. The number of such terms is NG) CN=20N-3) ew aag The denominator of this expression reflects the fact that interchanging i+ j,k «+ € ij) + (ke) gives the same term. The contribution from these torms is S4 3h NQEIN-1)iy-3) wn ONS cs Vey (Rady EOE ad, eeeThis rearranges into 2. ave . [arv(aue Py|sev9 yes] see a. Lar Sa eal This term is proportional to €4V2, ‘The reason for the extra power of V is clear: The two pairs of particles do not interact, so they can be arbitrarily far apart inside the volume of the gas. Hore is a general method of accounting the correction terms: Associate with each term a diagram in which the links represent factors of (e~*Y ~1) and vertices represent intoracting particles. Thus, we associate kev Coe te] os Lev Gade greMO] a. atv Cheney 4 VGEMN) | ome ee The factors of 2 in the denominators of the counting factors above are procisely the symmetry factors of the diagrams, that is, the number of ways that labels on the vertices can be interchanged without changing the diagram. We say that the first two diagrams are connected, that is, they contain a path along links from any vertex to any other vertex. The third diagram is disconnected, that is, there are some vertices that cannot be reached by moving along links from a given vertex. This diagram contains two connected components, Ibis simple to go from a diagram to its contribution to the grand partition function, The rules are 1. Give each vertex a factor €. 2. Give each connected component a factor V.wl Give each link a factor (e~°Y — 1) * Integrate over all relative coordinates. Divide by the symmetry factor S, defined above. . For example, the diagram has S =3!. Its value is + -BVA}) NG -BNG Goa he (e* 51 ee WE @NAy 1) Now we can write the complete value of © as a diagrammatic expansion ‘There is a further possible simplification. Notice that each disconnected diagram. can be written as the product of its connected components, perhaps divided by a symmetry factor. For example, [=] = 4m IS] > teal>More generally, -_ ' — |: t ” ‘ = + [errs = : ml ts J ™ ‘Then the particular sum of diagrams 1s ea sf) +[B]e- oh sums to an exponential = SE cy [el] mo If a disconnected diagram contains connected components of different types, it still factorizes, [>a] - esata Oc euee Sle OVC 76) ile (ST) * CAateds [Ba oe Each term is an exponential, and so T= wep [B+ bd + EC) +P] -]or St tg BV lam q emated Bago) ‘This rearrangement is called the exponentiation of the disconnected diagrams, If this is your first encounter with diagrammatic perturbation theory, please take note of this trick. You will see it again and again in setting where diagrams are used to represent interactions. To compute ®, we take the logarithm of this expression. ‘Then 2 = - STV -T: Comm 4 crmacted dagrams ) ‘This very compact expression is called the Mayer cluster expansion. In zeroth order. as we saw above, it gives Se n + Olvt) This means that a diagram with m vertices is of order n”. ‘Thus, the series is easily arranged into an expansion in powers of n. The first few terms are €- -8TV - Ths) - Tip al-.- Sim) OW) “Oue) As yet, n appears only implicitly. To make the dependence on n explicit, we need to eliminate £ in favor of n. I will now carry out this analysis explicitly to the level needed to compute the first virial coefficient B(T). The explicit expression for ® up to order n? is is2 N= -S x2 9 = gy a SV S&C ae ‘This equation can be solved for € in an expansion for small n Se n- ek KE MP) ee ‘Then, plugging this result back into @, we have . 2 oo OMe) Se - nV + Tw V CEM. Since © = —pV, we find for the equation of state a i> eve TT L ~ . pen [1-42 WE t IEV(r) is repulsive, the factor (e~*" —1) will be negative. Then the correction to the pressure is positive and we obtain a stiffer equation of state of n increases. If V(r) is attractive, we obtain a softer equation of state. For a potential with both attractive and repulsive parts, the competition between these effects is temperature-dependent. In particular, the attractive terms are exponentially enhanced and therefore more important at low temperatures. We will see later in the course that: this softening can have a dramatic effect, leading to a transition from the gas to the liquid state. 12