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Let $c_n$ count $n$-step self-avoiding walks on the square lattice from one fixed graph vertex. Splitting a self-avoiding walk after $m$ steps and dropping the avoidance constraint on its suffix gives $c_{m+n}\le c_m{c}_n$. The Fekete lemma therefore gives the connective constant $\mu =\lim c_n^{1/n}$. The planar dual graph of the square lattice is a translated copy of it, so its connective constant is also $\mu$.

Put $q=1-p$ and assume $q\mu <1$. Choose $a>\mu$ with $qa<1$. The definition of the connective constant provides a finite $K$ such that $c_j\le K{a}^j$ for every $j\ge 0$. A simple dual graph cycle of length $\ell$ surrounding $0$ has a graph vertex in a box of radius $\ell +1$: its diameter is at most $\ell$, and its coordinate ranges straddle the origin. Choose such a graph vertex as the starting point, orient the graph cycle, and omit its closing edge. The remaining self-avoiding walk has length $\ell -1$. Consequently the number $N_{\ell }$ of these graph cycles obeysfor fixed finite constants. A specified graph cycle is open in dual bond percolation, equivalently all its crossed primal edges are closed, with probability $q^{\ell }$. HenceTo make this tail argument valid for every $q\mu <1$, rather than only extremely small $q$, use a finite modification of Bernoulli percolation. Condition all primal edges within ${\Lambda }_N$ to be open. This event has positive probability for $p>0$. If the resulting percolation cluster of $0$ is finite, its outer boundary contains a simple closed dual graph cycle surrounding the whole box. Such a graph cycle has length tending to infinity with $N$ and crosses no forced-open edge. Under the conditioning its remaining edge states retain the original independent law, so its probability is still $q^{\ell }$. Choose $N$ so that the above tail is less than $1/2$. The conditional probability that $0$ belongs to an infinite percolation cluster is then at least $1/2$, and thus $\theta (p)>0$.

This connective-constant Peierls bound proves that every $p>1-{\mu }^{-1}$ is above or at the onset of positive percolation probability. Taking the infimum givesThe case $p=1$ is immediate. This proof uses the Peierls argument, without assuming the exact Harris-Kesten theorem.

Write ${\mathcal{W}}_n$ for the deterministic set of $n$-step self-avoiding walks from $0$. Each uses $n$ distinct edges, so independence givesFor $n\ge 1$, the function $t\mapsto t^{1/n}$ on $[0,\infty )$ is a concave function. The Jensen inequality gives the root-moment bound for open self-avoiding walksEquivalently, the Lyapunov moment inequality compares exponents $1/n$ and $1$, both strictly positive. Taking the limit superior and the connective constant limit provesThis includes $p=0$ and $n=1$. No independence between the different self-avoiding walk indicators is asserted or needed.

Splitting any $(m+n)$-step self-avoiding walk after $m$ steps and translating its remaining segment to the origin injects it into an ordered pair of an $m$-step and an $n$-step self-avoiding walk. Hence $b_{m+n}\le b_m{b}_n$. The sequence $a_n=\log b_n$ is subadditive, so the Fekete lemma givesExponentiating proves existence of the connective constant $\kappa ={\lim }_n{b}_n^{1/n}$.

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.

For the usual interpretation of a real chain in a good solvent, the detachment force is smaller in the weak-adsorption regime. Excluded volume swells the chain, increasing the cost of confinement near the substrate. The adsorbed layer becomes thicker and its binding free energy per monomer decreases. The same contact energy therefore does not mean the same total binding strength.

The scaling argument can include both adsorption and stretching. Let $\xi \sim b{g}^{\nu }$, where $\nu =1/2$ for an ideal chain and approximately $3/5$ for a self-avoiding walk in three dimensions. With the same contact-fraction approximation,Minimization gives $\xi /b\sim {ϵ}^{-\nu /(1-\nu )}$ and $\mu /(k_{B}T)\sim {ϵ}^{1/(1-\nu )}$. At detachment, a tensile blob of size ${\xi }_t\sim k_{B}T/f$ costs approximately $k_{B}T$; its monomer count is $g_t\sim ({\xi }_t/b{)}^{1/\nu }$. Equating the stretching gain per monomer $k_{B}T/g_t$ to $\mu$ givesThus $f_{\mathrm{real}}\sim (k_{B}T/b){ϵ}^{3/2}$, compared with $f_{\mathrm{ideal}}\sim (k_{B}T/b)ϵ$, so their ratio scales as ${ϵ}^{1/2}<1$ for weak attraction. These are scaling relations, not exact prefactors. The real-chain adsorption exponents here use the same simple uniform-contact model as the earlier parts; a more detailed surface theory of critical phenomena can refine them. The thicker, more weakly bound layer reflects the higher cost of confining a good solvent chain.^[ref]

“Real” alone does not specify solvent quality: a collapsed chain in a poor solvent, strong adsorption, or substantial bending stiffness requires a different comparison. The smaller-force conclusion concerns the flexible good solvent chain implicit in the excluded-volume correction.

In a slit, a confinement blob is three-dimensional but the chain of blobs forms a two-dimensional self-avoiding walk. With $g\sim (D/b{)}^{5/3}$ and in-plane exponent $3/4$, $R_{\parallel }\sim D(N/g{)}^{3/4}$. There is no single preferred axial extension as in a tube. A strictly planar chain confined further to a narrow strip is a different geometry and gives $X\sim L(b/D{)}^{1/3}$ under the two-dimensional blob estimate.

In independent bond percolation on a graph, let $c_n$ be the number of $n$-step self-avoiding walks from a fixed graph vertex and ${\kappa }_n$ the number that are open. Then $\mathbb{E}{\kappa }_n=c_n{p}^n$. The Jensen inequality for the concave function $t^{1/n}$ gives $\mathbb{E}({\kappa }_n^{1/n})\le p{c}_n^{1/n}$. No independence between different self-avoiding walk indicators is needed. When $c_n^{1/n}\to \mu$, the limit superior is at most $p\mu$.

An $n$-step self-avoiding walk on a graph is a sequence $v_0,\dots ,v_n$ of distinct graph vertices with an edge between successive graph vertices. It is a graph path with $n$ edges and $n+1$ graph vertices. On a transitive graph, the exponential growth rate of rooted self-avoiding walk counts is the connective constant.

The generating function weights each self-avoiding walk by $x$ to the power of its length, including the zero-length walk. Its radius of convergence is the reciprocal of the upper exponential growth rate of the rooted counts, by the Cauchy-Hadamard theorem.

Replace every degree-three vertex of a graph in one class of a bipartite graph by a triangle with one port for each incident edge. A self-avoiding walk whose endpoints remain in the other class cannot make two completed passages through the same triangle: each passage needs two unused ports and only three exist. Each old two-edge passage has exactly two replacements, of lengths three and four. Therefore the restricted generating functions satisfy $Z_H^0(x)=Z_G^0(\sqrt{x^3+x^4})$. If the old radius is $1/\mu$, the new radius obeys ${\rho }^3+{\rho }^4={\mu }^{-2}$.

For an infinite connected locally finite graph with a uniform degree bound, let ${\sigma }_n(v)$ count its length-$n$ self-avoiding walks from $v$. The suprema satisfy ${\sigma }_{m+n}\le {\sigma }_m{\sigma }_n$, so the Fekete lemma applied to their logarithms gives a finite connective constant. Unlike the usual rooted definition on a vertex-transitive graph, this definition explicitly takes the supremum over roots.

A graph whose automorphisms act transitively on its vertices: any chosen vertex of a graph can be carried to any other by a symmetry preserving adjacency. Consequently rooted self-avoiding walk counts are independent of the chosen root.

For independent bond percolation on the cubic lattice, define ${\tau }_p(x,y)={\mathbb{P}}_p(x\leftrightarrow y)$ and $g_n={\mathbb{P}}_p(0\leftrightarrow \partial {\Lambda }_n)$, with $g_0=1$. Split an open self-avoiding walk at its first radius-$m$ boundary vertex $y$. The remaining segment reaches distance at least $n-m$ from $y$, using disjoint edges. The BK inequality, translation invariance and the union bound yield the displayed estimate. Keeping the individual connection weights can be stronger than replacing their sum by $|\partial {\Lambda }_m|g_m$.