How Do You Calculate Free Energy for Gas Atoms Adsorbed on a Metal Surface?

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In summary: This will allow you to simplify the expression and use the fact that ##k_{B}T\ln(M!) \approx Mk_{B}T\ln(M)##. Additionally, you can use the fact that ##e^{\beta \Delta} = y## and from there, you can get the final expression for the free energy. In summary, the free energy of a metal surface with N ≫ 1 atoms adsorbed on M > N adhesion sites can be calculated using the Stirling approximation and the equation F = −N∆ + MkBT[(1 − y) ln(1 − y) + y ln y], where y = N/M.
  • #1
TroyElliott
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Originally posted in a technical forum section, so no HW template
The problem goes as follows... "

One model for the adsorption of gas atoms on a metal surface approximates the surface to be a corregated muffin-tin potential. A gas atom can lower its energy by sitting in one of the potential minima which are the adhesion sites on the surface each with a binding energy ∆. Ignore all other interactions. Show that the free energy of exactly N ≫ 1 atoms adsorbed to a metal surface with M > N adhesion sites is

F = −N∆ + MkBT[(1 − y) ln(1 − y) + y ln y],

where y = N/M."

My attempt at this problem goes as follows. This is a two level energy system, say with energy of 0 defined at the non-binding parts of the muffin-tin and ##-\Delta## in the binding wells. We can then write our partition function as follows,

$$Z = \binom{M}{0}+\binom{M}{1}e^{\beta \Delta}+\binom{M}{2}e^{\beta 2\Delta}+...+\binom{M}{N}e^{\beta N\Delta},$$

where ##\binom{M}{N}## is defined as ##\frac{M!}{N!(M-N)!}.##

This can be written as a series given by $$Z = \sum_{k=0}^{N}\binom{M}{k}e^{k\beta \Delta}.$$

When can be slightly further simplified to $$\ln{Z} = \ln{(M!)}+\ln{(\sum_{k=0}^{N}\frac{e^{k\beta \Delta}}{k!(M-k)!})}.$$

I know that the free energy is given by ##F = -k_{b}T\ln{(Z)}##, but I am not sure how to simplify the sum in order to get the correct free energy. Any ideas on where to go from here would be very much appreciated.

Thanks!
 
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  • #2
Since N ≫ 1, you can use the Stirling approximation.
 

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