Let a segment of fixed length make angle with an applied force . Its energy contribution is . Independent freely jointed orientations give the single-segment partition function and chain partition function
The mean end-to-end projection is the force derivative of :
For , the Langevin function is . Isotropy therefore gives the vector response
The covariance at zero force provides an independent route: , and the Boltzmann weight's first-order term yields . This is a relation for the mean vector or its projection. The zero-force mean vector vanishes even though the chain has finite root mean square size .
The controlled weak-force condition is , not merely that a short part of a measured curve looks straight. With the supplied , at . A raw force near , as in the figure's labelled low-extension portion, would give and is not asymptotically weak for those literal segment parameters. A force offset or different effective model might change that interpretation, but no such correction should be invented from the plot.
On releasing the tensile load, the extended chain first retracts towards less aligned conformations because they have much greater configurational multiplicity. Viscous friction and internal relaxation determine the time course; stored free energy is dissipated as heat. An unconstrained ideal chain does not shrink to a point: its mean vector is zero but its root mean square end-to-end length is for the supplied ideal-chain parameters.
A real polypeptide also has sequence-dependent interactions. If the original native structure is the stable state in the prevailing solvent and the molecule remains intact and capable of folding, it can subsequently refold, gaining favourable intramolecular and solvent free energy. The folded state is not selected by chain entropy alone, and formation of native contacts need not be instantaneous. Kinetic traps, proline isomerization, protein aggregation, misfolding, surface attachments or chemical damage may prevent complete recovery or produce hysteresis. Thus reversible refolding is a physically motivated possibility, not guaranteed simply by removal of force. This distinction connects the recoil of a stretched polymer to the thermodynamics discussed in Question 6(c).
The integrand is positive, so the minimum-variance importance distribution is its target-weighted probability density function, normalized by :
By completing the square,
Thus is the multivariate normal distribution , where is the first standard basis vector. Its importance weight and weighted integrand are
A variance cannot be negative, and this proposal makes every summand constant, proving optimality directly. It is admissible under the arbitrary-proposal condition even though its mean vector is not zero. Although optimal proposals usually involve an unknown normalizing integral, here both that integral and the resulting normal distribution are explicit.