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For the three-dimensional worm-like chain, define the bending coefficient ${\kappa }_b$ by $F_b=({\kappa }_b/2)\int |{\partial }_s\mathbf{t}{|}^{2}ds$. Its persistence length is $l_p={\kappa }_b/(k_{B}T)$. Holding that coefficient and the polymer contour length $L$ fixed givesThe temperatures must be absolute. The end-to-end distance of a worm-like chain obeysFor a long flexible chain, $L\gg l_p$, the typical size is $R_{\mathrm{rms}}\simeq \sqrt{2L{l}_p}$, so warming contracts the chain, with $R_{\mathrm{rms}}(T_2)/R_{\mathrm{rms}}(T_1)\simeq \sqrt{T_1/T_2}$. The finite-length formula also decreases as $l_p$ decreases, but the rod limit $L\ll l_p$ changes very little. A large segment count alone does not guarantee $L\gg l_p$. If the material's bending coefficient itself depends on temperature, replace the first ratio by $[{\kappa }_b(T_2)/{\kappa }_b(T_1)]T_1/T_2$; the sign then needs that additional material information. This calculation concerns a generic physical filament, with no biomolecular application.

Polydispersity means that a sample contains chains of different molar masses or lengths. Let $n_i$ count chains with molar mass $M_i$. The number-average molar mass gives every chain equal weight, while the weight-average molar mass weights a chain population by its contribution to total mass:Writing $w_i=n_i{M}_i/{\sum }_j{n}_j{M}_j$ makes the latter interpretation explicit: $M_w={\sum }_i{w}_i{M}_i$. Large chains therefore influence $M_w$ more strongly. If brackets denote an average over chain number,The ratio is molar-mass dispersity, conventionally written Đ. It equals one only when every chain has the same molar mass. Different distributions can share the same ratio, so it does not specify the full distribution.

For a freely jointed chain, write the end-to-end vector as the sum of $N$ independently oriented steps ${\mathbf{b}}_i$, each of fixed length $a$. Isotropy gives $⟨{\mathbf{b}}_i⟩=0$, and independence gives $⟨{\mathbf{b}}_i\cdot {\mathbf{b}}_j⟩=0$ for $i\ne j$. HenceThe root-mean-square end-to-end distance of a polymer chain is $a\sqrt{N}$, although the mean vector is zero. Its polymer contour length is $L=Na$, an upper bound on extension; it is not the typical unforced end-to-end length.

Stiffness correlates neighboring bond directions, so the discarded cross terms need not vanish. A freely rotating chain fixes the angle $\theta$ between successive forward bond vectors but leaves torsion uniformly distributed. Set $q=\cos \theta$, so $⟨{\mathbf{b}}_i\cdot {\mathbf{b}}_{i+s}⟩=a^2{q}^s$. ThenFor a chain long compared with its orientational correlation range, the characteristic ratio of a freely rotating chain approaches $C_{\infty }=(1+q)/(1-q)$. Positive forward persistence increases the mean-square size and gives the Kuhn length of a freely rotating chain $b_K=a{C}_{\infty }$. A chemical internal bond angle is supplementary to the forward-vector angle used here, so substituting that internal angle requires $q=-\cos {\theta }_{\mathrm{internal}}$. For $q\to 1$ at fixed $N$, the finite sum tends to $N^2{a}^2$, the rigid-rod result; taking the long-chain limit first would incorrectly predict an unbounded size. Real torsional energy preferences can be represented by a rotational isomeric state model, with weighted torsional states and correlations beyond independent free rotations.

A worm-like chain describes continuously varying local orientation. For unit tangent $\mathbf{t}(s)$ and bending stiffness $\kappa$, its elastic energy is $E_b=(\kappa /2){\int }_0^L|d\mathbf{t}/ds{|}^{2}ds$. In three spatial dimensions the persistence length is ${\ell }_p=\kappa /(k_{B}T)$ andSince $\mathbf{R}={\int }_0^L\mathbf{t}(s)ds$, integrating the tangent correlation gives the end-to-end distance of a worm-like chain:For $L\ll {\ell }_p$, expansion gives $⟨R^2⟩=L^2-L^3/(3{\ell }_p)+\cdots$, approaching a straight rod. For $L\gg {\ell }_p$, it gives $⟨R^2⟩\simeq 2{\ell }_{p}L$, the long-chain ideal chain result with Kuhn length $2{\ell }_p$. These models isolate stiffness; long-range excluded volume can additionally swell an isolated chain in a good solvent. When coarse-graining, a chemical repeat count and a count of independent statistical steps must not be silently interchanged.

The first panel shows the exact worm-like chain crossover between a rod and a long flexible coil. The second compares original normalized scaling curves for a uniform polymer brush; their prefactors have been chosen for illustration and do not fit the exam's experimental points.

For a good solvent, consider long flexible grafted polymer chains with grafting density $\sigma$ and lateral spacing $D\sim {\sigma }^{-1/2}$. At high coverage, $D$ is smaller than the isolated coil size, and adjacent chains cannot retain their unperturbed conformations. A scaling model divides each chain into concentration blobs of diameter $D$. Inside one blob the chain retains good-solvent statistics,using the Flory approximation exponent $3/5$. The $N/g$ blobs per chain form a stretched sequence approximately normal to the surface. The good-solvent brush height therefore obeysHere $a$ and $N$ refer to consistently chosen effective segments, whose microscopic properties are held fixed as chain length changes. The result is a scaling law with an undetermined order-one prefactor, not a fully specified height in nanometres.

A complementary free-energy balance per chain iswhere $v>0$ is effective segment excluded volume. The first term is the chain entropy cost of stretching and the second is the cost of crowding segments into a layer of volume $h/\sigma$ per chain. Minimization gives $h^3\sim v{N}^3{a}^2\sigma$; with $v\sim a^3$ it recovers the same height. The blob argument incorporates good-solvent correlations more directly. Both descriptions require overlapping chains, many segments per chain, and heights below the polymer contour length; the power law cannot be extrapolated to infinite grafting density.

In the printed experimental graph, the vertical axis is $h{D}^2/(10^6{\mathring{\mathrm{A}}}^3)$ and the horizontal axis is $M/10^5$. The approximately straight trend through the origin therefore means $h{D}^2\propto M$. Since $D^{-2}\sim \sigma$ and $M$ is proportional to chain length for a fixed repeat chemistry,The dashed guide rises by roughly $1.8$–$1.9$ vertical units over six horizontal units, corresponding to $h{D}^2/M$ of order $3{\mathring{\mathrm{A}}}^3$ per unit of the plotted $M$. This is an approximate graphical slope, not a fitted material constant; the graph does not specify a numerical monomer count or a repeat-unit volume from which an absolute brush height could independently be calculated.

The poor-solvent brush height has a simple volume argument. Let $v_0$ be the volume per repeat and $\varphi$ the roughly fixed polymer volume fraction within a dense uniform layer. There are $N\sigma$ repeats per substrate area, soFor fixed poor-solvent conditions, $\varphi$ is approximately independent of $N$ and $\sigma$, giving the observed linear grafting-density dependence. Polymer–polymer contacts are favored and the layer becomes relatively compact; in a good solvent, favorable solvent contact and segment repulsion instead produce a swollen layer whose stretching and osmotic costs balance at the weaker ${\sigma }^{1/3}$ dependence. Sparse isolated polymer globules or lateral segregation fall outside the uniform-brush model.

The cited experimental paper's abstract independently reports these two scaling laws, but identifies polydimethylsiloxane chains on porous silicon dioxide, rather than the polystyrene system named in the exam. The solution uses the printed axes to infer the exponents and does not treat that material identification as verified experimental provenance.^[ref]

Ideal and self-avoiding walks. An ideal chain has independent isotropic coarse-grained steps and permits self-intersections in its mathematical model. For $N$ steps of length $b$, the cross terms average to zero, so its root-mean-square end-to-end distance of a polymer chain obeysA self-avoiding walk excludes repeated occupancy or intersection at the segment scale. This represents positive excluded volume in a dilute good solvent. The nonlocal constraint correlates otherwise distant portions of the chain and swells it:The Flory approximation replaces this exponent by $3/5$, by balancing stretching free energy $R^2/(N{b}^2)$ with an interaction contribution $v{N}^2/R^3$. The result is a more extended and less internally dense coil than the ideal walk; self-avoidance changes the statistics, not merely the local step length.

Two ideal-chain regimes. At the theta temperature for a dilute polymer–solvent pair, leading effective segment attractions and repulsions cancel. Large-scale chain statistics are approximately ideal, even though microscopic atoms still have finite size. In a homogeneous polymer melt, surrounding chains screen long-range excluded volume interactions of a chosen chain, again making its equilibrium large-scale size approximately ideal. Local bond-angle correlations must be included in an effective statistical length such as the Kuhn length. Polymer entanglements can slow the dynamics without invalidating this leading equilibrium size law.

Semiflexible DNA. The nucleic acid double helix gives double-stranded DNA a bending stiffness and substantial local orientational persistence. Independent step orientations are therefore a poor description on short scales, while self-avoidance alone does not specify the energy cost of bending. The worm-like chain describes the molecule as a continuously bendable, locally inextensible curve $\mathbf{r}(s)$ parameterized by arc length $s$, with unit tangent $\mathbf{t}(s)=d\mathbf{r}/ds$. Its bending energy iswhere $A$ is bending stiffness. In the free three-dimensional model, the persistence length is ${\ell }_p=A/(k_{B}T)$ andThus ${\ell }_p$ is the contour separation over which tangent alignment falls by the factor $e^{-1}$; it quantifies stiffness relative to thermal bending. The model bridges locally rod-like and globally coil-like conformations. It omits long-range self-avoidance in its simplest form, so sufficiently long dilute DNA can require excluded-volume corrections.

Flexible and rigid limits. Integrating the tangent correlation over the two contour positions gives the end-to-end distance of a worm-like chain:For a very flexible chain on the scale of its total length, $L/{\ell }_p\gg 1$, the exponential is negligible andThis is the ideal chain result with Kuhn length $b_K=2{\ell }_p$ and effective step count $N_K=L/(2{\ell }_p)$. Many persistent sections have decorrelated orientations. The flexible limit means a large ratio $L/{\ell }_p$ within the continuum model's range, not an extrapolation of the persistence length below all molecular length scales.

For a nearly rigid chain, $L/{\ell }_p\ll 1$, the constant and linear terms in the exponential cancel those outside it. The Taylor series givessoThis is the expected rod limit: all tangents are nearly aligned, and the end-to-end distance approaches the arc length.

Helix–coil curves. A helix-coil transition model allows ordered helical runs and disordered coil regions. Use $s$ and $\sigma$ with exactly the free-energy conventions defined in the paper. A negative $\Delta F_{\mathrm{hc}}$ gives $s>1$ and favors the helical state; a positive junction cost gives $0<\sigma <1$ and penalizes starting new domains. The supplied helical fraction is the long-chain form associated with the Zimm-Bragg model.

Its main features follow directly without assuming a sharp transition. Put $Q=(s-1{)}^2+4s\sigma$. For every $\sigma >0$,and differentiating givesThus all curves rise monotonically and cross at $(1,1/2)$. Increasing the boundary free-energy cost reduces $\sigma$, suppresses frequent coil–helix boundaries and makes longer runs favorable. The transition region becomes narrower and steeper: balancing $(s-1{)}^2$ against $4s\sigma$ gives a width of order $\sqrt{\sigma }$ near $s=1$.

For $\sigma =1$, the fraction simplifies to $\boxed{f_h=s/(1+s)}$, the noncooperative two-state result. For $0<\sigma \ll 1$, the steep curve describes cooperative helix formation. In the singular limit $\sigma \downarrow 0$, it approaches zero for $s<1$ and one for $s>1$; its midpoint remains $1/2$ when approached through positive $\sigma$. Setting $\sigma =0$ directly makes the formula indeterminate at $s=1$. For any fixed positive $\sigma$, the given long-chain curve is smooth: it is a cooperative crossover, not a true discontinuity. The plot varies $s$ at fixed $\sigma$; in an actual temperature scan both parameters may change, and a finite chain can further round the crossover.