1-dimensional hard rods

1-dimensional hard rods (sometimes known as a Tonks Gas ) consist of non-overlapping line segments of length $\sigma$ who all occupy the same line which has length $L$. One could also think of this model as being a string of hard spheres confined to 1 dimension (not to be confused with 3-dimensional hard rods). The model is given by the intermolecular pair potential:

$\Phi _{12}(x_{i},x_{j})=\left\{{\begin{array}{lll}0&;&|x_{i}-x_{j}|>\sigma \\\infty &;&|x_{i}-x_{j}|<\sigma \end{array}}\right.$

where $\left.x_{k}\right.$ is the position of the center of the k-th rod, along with an external potential; the whole length of the rod must be inside the range:

$V_{0}(x_{i})=\left\{{\begin{array}{lll}0&;&\sigma /2<x<L-\sigma /2\\\infty &;&{\mathrm {elsewhere} }.\end{array}}\right.$

Canonical Ensemble: Configuration Integral

The statistical mechanics of this system can be solved exactly. Consider a system of length $\left.L\right.$ defined in the range $\left[0,L\right]$. The aim is to compute the partition function of a system of $\left.N\right.$ hard rods of length $\left.\sigma \right.$. Consider that the particles are ordered according to their label: $x_{0}<x_{1}<x_{2}<\cdots <x_{N-1}$; taking into account the pair potential we can write the canonical partition function (configuration integral) of a system of $N$ particles as:

${\frac {Z\left(N,L\right)}{N!}}=\int _{\sigma /2}^{L+\sigma /2-N\sigma }dx_{0}\int _{x_{0}+\sigma }^{L+\sigma /2-N\sigma +\sigma }dx_{1}\cdots \int _{x_{i-1}+\sigma }^{L+\sigma /2-N\sigma +i\sigma }dx_{i}\cdots \int _{x_{N-2}+\sigma }^{L+\sigma /2-N\sigma +(N-1)\sigma }dx_{N-1}.$

Variable change: $\left.\omega _{k}=x_{k}-\left(k+{\frac {1}{2}}\right)\sigma \right.$ ; we get:

${\frac {Z\left(N,L\right)}{N!}}=\int _{0}^{L-N\sigma }d\omega _{0}\int _{\omega _{0}}^{L-N\sigma }d\omega _{1}\cdots \int _{\omega _{i-1}}^{L-N\sigma }d\omega _{i}\cdots \int _{\omega _{N-2}}^{L-N\sigma }d\omega _{N-1}.$

Therefore:

${\frac {Z\left(N,L\right)}{N!}}={\frac {(L-N\sigma )^{N}}{N!}}.$

$Q(N,L)={\frac {(L-N\sigma )^{N}}{\Lambda ^{N}N!}}.$

Thermodynamics

Helmholtz energy function

$\left.A(N,L,T)=-k_{B}T\log Q\right.$

In the thermodynamic limit (i.e. $N\rightarrow \infty ;L\rightarrow \infty$ with $\rho ={\frac {N}{L}}$, remaining finite):

$A\left(N,L,T\right)=Nk_{B}T\left[\log \left({\frac {N\Lambda }{L-N\sigma }}\right)-1\right].$

Equation of state

Using the thermodynamic relations, the pressure (linear tension in this case) $\left.p\right.$ can be written as:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle p = - \left( \frac{ \partial A}{\partial L} \right)_{N,T} = \frac{ N k_B T}{L - N \sigma}; }

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z = \frac{p L}{N k_B T} = \frac{1}{ 1 - \eta}, }

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \eta \equiv \frac{ N \sigma}{L} } ; is the fraction of volume (i.e. length) occupied by the rods.

It was shown by van Hove that there is no fluid-solid phase transition for this system (hence the designation Tonks gas).

Isobaric ensemble: an alternative derivation

Adapted from Reference . If the rods are ordered according to their label: Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle x_0 < x_1 < x_2 < \cdots < x_{N-1} } the canonical partition function can also be written as:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z= \int_0^{x_1} d x_0 \int_0^{x_2} d x_1 \cdots \int_0^{L} d x_{N-1} f(x_1-x_0) f(x_2-x_1) \cdots f(L-x_{N-1}), }

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle N!} does not appear one would have Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle N!} analogous expressions by permuting the label of the (distinguishable) rods. Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle f(x)} is the Boltzmann factor of the hard rods, which is Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 0} if Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle x<\sigma} and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 1} otherwise.

A variable change to the distances between rods: Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle y_k = x_k - x_{k-1} } results in

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z = \int_0^{\infty} d y_0 \int_0^{\infty} d y_1 \cdots \int_0^{\infty} d y_{N-1} f(y_1) f(y_2) \cdots f(y_{N-1}) \delta \left( \sum_{i=0}^{N-1} y_i-L \right): }

the distances can take any value as long as they are not below Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \sigma} (as enforced by Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle f(y)} ) and as long as they add up to Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle L} (as enforced by the Dirac delta). Writing the later as the inverse Laplace transform of an exponential:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z = \int_0^{\infty} d y_0 \int_0^{\infty} d y_1 \cdots \int_0^{\infty} d y_{N-1} f(y_1) f(y_2) \cdots f(y_{N-1}) \frac{1}{2\pi i } \int_{-\infty}^{\infty} ds \exp \left[ - s \left(\sum_{i=0}^{N-1} y_i-L \right)\right]. }

Exchanging integrals and expanding the exponential the Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle N} integrals decouple:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z = \frac{1}{2\pi i } \int_{-\infty}^{\infty} ds e^{ L s } \left\{ \int_0^{\infty} d y f(y) e^{ - s y } \right\}^N. }

We may proceed to invert the Laplace transform (e.g. by means of the residues theorem), but this is not needed: we see our configuration integral is the inverse Laplace transform of another one,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z'(s)= \left\{ \int_0^{\infty} d y f(y) e^{ - s y } \right\}^N, }

so that

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z'(s) = \int_0^{\infty} ds e^{ L s } Z(L). }

This is precisely the transformation from the configuration integral in the canonical (Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle N,T,L} ) ensemble to the isobaric (Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle N,T,p} ) one, if one identifies Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle s=p/k T} . Therefore, the Gibbs energy function is simply Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle G=-kT\log Z'(p/kT) } , which easily evaluated to be Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle G=kT N \log(p/kT)+p\sigma N} . The chemical potential is Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mu=G/N} , and by means of thermodynamic identities such as Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \rho=\partial p/\partial \mu} one arrives at the same equation of state as the one given above.

References

Related reading

• L. van Hove "Quelques Propriétés Générales De L'intégrale De Configuration D'un Système De Particules Avec Interaction", Physica, 15 pp. 951-961 (1949)
• Zevi W. Salsburg, Robert W. Zwanzig, and John G. Kirkwood "Molecular Distribution Functions in a One-Dimensional Fluid", Journal of Chemical Physics 21 pp. 1098-1107 (1953)
• Robert L. Sells, C. W. Harris, and Eugene Guth "The Pair Distribution Function for a One-Dimensional Gas", Journal of Chemical Physics 21 pp. 1422-1423 (1953)
• Paolo V. Giaquinta "Entropy and Ordering of Hard Rods in One Dimension", Entropy 10 pp. 248-260 (2008)