1-dimensional hard rods

1-dimensional hard rods (sometimes known as a Tonks Gas ) consist of non-overlapping line segments of length 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} who all occupy the same line which has length 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} . 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:

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 \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 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 \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:

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 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 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 \left[ 0, L \right] } . The aim is to compute the partition function of a system of 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 \left. N \right. } hard rods of length 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 \left. \sigma \right. } . Consider that the particles 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} } ; taking into account the pair potential we can write the canonical partition function (configuration integral) of a system of 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 } particles 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 \frac{ Z \left( N,L \right)}{N!} = \int_{\sigma/2}^{L+\sigma/2-N\sigma} d x_0 \int_{x_0+\sigma}^{L+\sigma/2-N\sigma+\sigma} d x_1 \cdots \int_{x_{i-1}+\sigma}^{L+\sigma/2-N\sigma+i \sigma} d x_i \cdots \int_{x_{N-2}+\sigma}^{L+\sigma/2-N\sigma+(N-1)\sigma} d x_{N-1}. }

Variable change: 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 \left. \omega_k = x_k - \left(k+\frac{1}{2}\right) \sigma \right. }  ; we get:

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 \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:

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

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

Thermodynamics

Helmholtz energy function

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 \left. A(N,L,T) = - k_B T \log Q \right. }

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

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 A \left( N,L,T \right) = N k_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) 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 \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}; }

$Z={\frac {pL}{Nk_{B}T}}={\frac {1}{1-\eta }},$

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.

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 $N!$ 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)
• L. van Hove, "Sur L'intégrale de Configuration Pour Les Systèmes De Particules À Une Dimension", Physica, 16 pp. 137-143 (1950)
• 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)