Ideal chain

An ideal chain, also called a freely jointed chain, consists of fixed-length links with independent orientations and no bending energy between successive links. It neglects segment interactions and excluded volume. A one-dimensional freely jointed chain restricts each link to two orientations. At fixed force its canonical partition function factors into one-link angular integrals. The resulting extension is entropic and depends on temperature and on whether the orientations are allowed in one, two, or three dimensions.

A freely jointed chain supplemented with axial segment compliance. A simple phenomenological additive law is $z=L\mathcal{L}(fb/(k_{B}T))+Lf/S$, where $L=Nb$, $\mathcal{L}$ is the Langevin function and $S$ is an axial stretch modulus with units of force. This adds energetic compliance to the entropic spring; it is not an exact angular average for arbitrary harmonic-link statistics.

A freely rotating chain has fixed bond length and fixed angle between successive forward bond vectors, with independently uniform torsion angles. It neglects interactions between distant chain segments. The fixed angle introduces short-range orientational correlations even though the torsional rotations are unrestricted. Its characteristic ratio of a freely rotating chain converts those correlations into an end-to-end size; its equivalent long-chain link is the Kuhn length of a freely rotating chain.

With independently uniform torsion, consecutive forward tangent correlations multiply by $\cos \vartheta$. After $n$ bonds the correlation is $(\cos \vartheta {)}^n$. Matching it to $e^{-nb/{\ell }_p}$ gives the displayed decay length for positive correlation. This discrete orientational definition need not equal half the equivalent Kuhn length exactly.

For $N$ bonds of length $a$, fixed forward angle $\theta$ and uniform independent torsions, conditional averaging gives $⟨{\mathbf{a}}_i\cdot {\mathbf{a}}_j⟩=a^2{\alpha }^{|j-i|}$. Consequently $⟨R^2⟩=N{a}^2+2a^2{\sum }_{k=1}^{N-1}(N-k){\alpha }^k$. Dividing by the independent-step result $N{a}^2$ and summing the geometric series gives the displayed $C_N$, for $\alpha \ne 1$. For fixed $|\alpha |<1$, $C_N\to C_{\infty }=(1+\alpha )/(1-\alpha )$.

The angle is measured between forward vectors; a chemical internal bond angle is supplementary. At $\alpha =1$, the finite chain is a rigid rod with $C_N=N$, so taking the infinite-chain limit before the rigid limit would be invalid. The Kuhn length of a freely rotating chain is asymptotically $a{C}_{\infty }$.

For an ideal chain of $N$ independent statistical segments of length $a$, the end-to-end probability density is proportional to $\exp [-3R^2/(2N{a}^2)]$. Its constrained Helmholtz free energy has extension-dependent part $3k_{B}T{R}^2/(2N{a}^2)$, so the restoring force is $-3k_{B}T\mathbf{R}/(N{a}^2)$. This is an entropic spring because extension removes available chain configurations, and its stiffness grows with temperature. The Gaussian law applies at extensions small compared with the contour length $Na$; near full extension, finite extensibility matters.

Entropic elasticity is a restoring response arising from the reduction of accessible molecular configurations under deformation. For an ideal freely jointed chain, weak extension has free energy $\Delta \mathcal{F}=3k_{B}T{R}^2/(2N{b}^2)$ and spring constant $k=3k_{B}T/(N{b}^2)$. The proportionality to temperature assumes fixed segment geometry; temperature-dependent Kuhn length modifies it.

An ideal chain with endpoint charges $+q$ and $-q$ has coupling energy $-q\mathbf{E}\cdot \mathbf{R}$ in a uniform electric field, when $\mathbf{R}$ points from negative to positive charge. Completing the square in its Gaussian end-to-end distribution gives the displayed mean extension. The force conjugate to end separation is $qE$, even though the two endpoints experience opposite forces; adding their magnitudes would double-count the work. The zero-field rms length is $a\sqrt{N}$, and the rms of a single Cartesian component is $a\sqrt{N/3}$. Direct endpoint interactions and charge-induced changes of solvent quality are excluded from this model.

An effective step length describing a specified chain-count convention: an ideal polymer with $N$ counted units has mean-squared end-to-end distance of a polymer chain $⟨R^2⟩=N{b}^2$. If $N$ counts freely jointed coarse-grained units, $b$ is their Kuhn length. If $N$ counts chemical repeat units, the effective $b$ incorporates local conformational correlations and is not automatically a physical monomer diameter. A repeat-unit volume $v_0$ is independent information; setting $v_0\sim b^3$ is a scaling approximation.

For $N$ independent links pointing left or right with length $a$, fixed signed extension $L$ gives $N_R=(N+L/a)/2$ and $N_L=(N-L/a)/2$. The multiplicity is $\left(\genfrac{}{}{0ex}{}{N}{N_L}\right)$ when these counts are nonnegative integers. Leading Stirling's approximation gives $\mathcal{F}=(k_{B}T/(2a))\ln (N_R/N_L)$ as the externally applied tension conjugate to $L$. Its small-extension limit is $k_{B}TL/(N{a}^2)$. At fixed tension, the exact one-link partition function is $2\cosh (\beta \mathcal{F}a)$ and the mean extension is $Na\tanh (\beta \mathcal{F}a)$, confirming the same inverse relation without using Stirling at the full-extension endpoint.

The exact count is $\Omega =\left(\genfrac{}{}{0ex}{}{N}{q}\right)=N^q{\prod }_{j=0}^{q-1}(1-j/N)/q!$. For fixed $q$ and large $N$, this is asymptotic to $N^q/q!$. Uniform relative accuracy requires $q^2/N\ll 1$, since the logarithm of the product starts at $-q(q-1)/(2N)$. The weaker assumption $q/N\ll 1$ gives the leading sparse-link entropy but need not give a small relative multiplicity error. In the continuum range $1\ll q\ll N$, the entropic force behaves as $(k_{B}T/(2a))\ln (N/q)$. The fixed-tension mean extension approaches $Na$ only as the tension diverges; at the discrete endpoint $q=0$ the exact entropy is zero and a continuous fixed-extension derivative is not defined.

A three-dimensional ideal chain of $N$ independent segments of length $b$ has $⟨R^2⟩=N{b}^2=Lb$. The isotropic small-force susceptibility gives $⟨z⟩=F⟨R^2⟩/(3k_{B}T)$, so $k_s=3k_{B}T/(Lb)$. For a long worm-like chain, the statistical segment is $b=2l_p$. This stiffness describes entropic end-to-end extension, not axial stretching of the material backbone, whose spring constant is $EA/L$.

For an isotropic fixed-length step $b$, angular integration gives the characteristic function $\hat{\psi }(\mathbf{k})=\sin (kb)/(kb)$. Independence makes the characteristic function of the sum of $N$ steps its $N$th power. Since $\ln [\sin (kb)/(kb)]=-k^2{b}^2/6+O(k^4{b}^4)$, the central scaling $k=O((b\sqrt{N}{)}^{-1})$ gives $\hat{\Phi }\to \exp [-N{b}^2{k}^2/6]$. The inverse Fourier transform isThis is a density with respect to three-dimensional vector volume, not a radial density; the radial density is $4\pi R^2\Phi$. It has $⟨R^2⟩=N{b}^2$. The approximation holds on the central coil scale $R=O(b\sqrt{N})$, not near the fully stretched finite-length boundary $R=Nb$.

If each link is restricted to a plane, $Z_1={\int }_0^{2\pi }{e}^{\xi \cos \theta }d\theta =2\pi I_0(\xi )$, with $\xi =Fb/(k_{B}T)$. Differentiating gives $L/(Nb)=I_1(\xi )/I_0(\xi )$, where $I_n$ are Modified Bessel functions of the first kind. The high-force angular Gaussian has $⟨{\theta }^2⟩\sim 1/\xi$, so $Nb-L\sim N{k}_{B}T/(2F)$, half the three-dimensional coefficient.

Independent link orientations make the canonical partition function $Z_1^N$, with the one-link integral defining the Langevin function. Differentiating its logarithm with respect to force gives $L=Nb\mathcal{L}(Fb/(k_{B}T))$. At high extension, $Nb-L\sim N{k}_{B}T/F$, so the force diverges inversely with remaining length deficit. This requires rigid links and excludes axial bond stretching.

The Langevin function is the mean projection of a freely orientable three-dimensional unit vector weighted by $e^{\xi \cos \theta }$. Integrating over solid angle gives $Z_1=4\pi \sinh \xi /\xi$, and differentiation gives $⟨\cos \theta ⟩={\partial }_{\xi }\log Z_1=\coth \xi -1/\xi$. It behaves as $\xi /3$ at small argument and $1-1/\xi$ at large positive argument.