Past exam of the mathematics course of the University of Cambridge 2017 iii Paper 344 1 d Solution Created 2026-10-03 Updated 2026-10-06
The post-quench Ornstein-Uhlenbeck process has . Its future noise is independent of the initial field. Consequently the cross term between the initial Fourier mode and its future noise integral has zero expectation. The Itô isometry, or the given white-noise covariance, then yieldsThe initial Gaussian Boltzmann distribution, with , gives in the same unitary normalization. Thus the Gaussian Model A quench hasThe static structure factor interpolates monotonically mode by mode between its two positive equilibrium values. The covariance relaxes at twice the amplitude decay rate. These statements assume that , and are unchanged by the quench; both exclude a spinodal instability.
Past exam of the mathematics course of the University of Cambridge 2018 iii Paper 344 1 c Solution Created 2026-10-03 Updated 2026-10-05
At thermal equilibrium, microscopic reversibility equates the probabilities of a path and its reversed path when both include their Boltzmann distribution initial weights. Denote their endpoint states by , including velocity if needed. Since the Hamiltonian is even under time reversal in classical mechanics,This detailed balance condition and the energy balance for an autonomous Lagrangian yieldThis is the fluctuation-dissipation relation for a Langevin particle: the strength of Gaussian white noise is fixed by the damping and temperature, with the Boltzmann constant.
For an equilibrium coarse-grained variable, the unresolved microscopic states contribute entropy; their statistical weight is encoded in the Helmholtz free energy, rather than in a single microscopic energy. Relative to the same reference measure, , so microscopic reversibility becomesThis extension assumes an equilibrium coarse-grained description with reversible path statistics; externally driven dynamics need not obey this relation.
Past exam of the mathematics course of the University of Cambridge 2018 iii Paper 344 1 e Solution Created 2026-10-03 Updated 2026-10-14
For and , each Fourier mode is an Ornstein-Uhlenbeck process with decay rate . Its explicit Ornstein-Uhlenbeck solution isso the Itô isometry givesTo identify the overdamped Langevin dynamics, choose a friction , a harmonic oscillator potential , and force noise . The fluctuation-dissipation relation for a Langevin particle then defines . Its Boltzmann distribution isThis is the stationary spectrum of a linear fluctuating interface, also following from the equipartition theorem. The numerical prefactor uses exactly the mode-noise normalization given in the paper. The nonzero modes can therefore have a stationary Gaussian distribution even though the unpinned zero mode cannot.
Past exam of the mathematics course of the University of Cambridge 2021 iii Paper 344 4 b Solution 2026-09-29
The Fluctuation-dissipation theorem for mobility requiresComparison with the stated noise amplitude givesThis choice makes the stationary Fokker-Planck equation have the Boltzmann distribution proportional to .
Past exam of the mathematics course of the University of Cambridge 2022 iii Paper 344 3 c Solution 2026-09-28
Detailed balance says that each equilibrium transition is balanced by its time reverse:With the Boltzmann distribution and , this requiresParts a and b instead give . Equality for every pair of endpoints yields the fluctuation-dissipation relation for a Langevin particle
For an admissible nonzero real trial function, integration by parts and the zero-flux boundary conditions reduce the Rayleigh quotient toA nonzero constant trial function attains zero. Positivity of also shows that equality requires . HenceIf the conserved total amount is , the normalized stationary solution isIts diffusive flux vanishes everywhere. The Boltzmann distribution fixes the spatial profile, while the diffusivity affects the relaxation toward it. Boundedness of makes the normalization finite on this finite interval.
A Gaussian distribution with mean and standard deviation has probability densityIts symmetry, finite variance and simple behavior under linear combinations make it useful for repeated measurements. Roughly , and of observations lie within one, two and three true standard deviations of the mean. These are coverage probabilities for a specified distribution, not guarantees that every experimental error is normal.
Why it appears. The central limit theorem explains why many sums of small independent finite-variance contributions approach a Gaussian law after centering and scaling, provided no single contribution dominates. Detector noise, small mechanical disturbances and multiple electronic fluctuations can combine approximately this way. The theorem does not remove a common calibration bias, and it does not justify assuming normal tails for rare large disturbances or arbitrarily correlated errors. A large-mean Poisson distribution also approaches a Gaussian with variance equal to its mean, making normal approximations useful for high-count photon or particle data; low counts require the discrete model.
A classical particle at thermal equilibrium in a one-dimensional harmonic potential has a Gaussian position distribution directly from the Boltzmann distribution:Thus a Gaussian law can arise from the energy dependence of equilibrium probability, rather than only from an informal appeal to many independent errors.
Precision of repeated measurements. For independent observations with the same mean and variance, the sample mean has variance . For Gaussian observations this mean is exactly Gaussian:Consequently quadrupling the number of independent readings halves the random standard error. When the true variance is unknown, a small-sample confidence interval for a normal mean uses a Student t-distribution with statistical degrees of freedom; replacing that by a normal quantile can overstate precision. Shared systematic errors and correlations do not decrease by the same averaging rule.
Combining results and fitting models. Independent Gaussian estimates of one quantity, with known variances , combine through the inverse-variance weighted meanFor a model with independent zero-mean Gaussian noise, maximizing the likelihood is equivalent to minimizing the weighted least-squares statisticFor a correct linear model with known independent Gaussian errors and fitted parameters of full rank, the minimized statistic has a chi-squared distribution with degrees of freedom. Nonlinear fits only inherit that familiar approximation under additional regularity and adequate-data assumptions. Known correlated Gaussian errors require the full inverse covariance matrix in the quadratic form.
These properties support confidence intervals, consistency checks, calibration and error propagation. They also give practical diagnostics: inspect residuals for trends, changing spread, correlations or outliers before trusting a Gaussian fit. Gaussian models connect physical fluctuations to quantitative uncertainty, but their assumptions must be checked rather than inferred from the shape of a convenient bell curve.
Past exam of the physics A course of the University of Cambridge 2021 Paper 1 Section D D9 Solution 2026-10-18
The photoelectric effect, black-body radiation and the Davisson–Germer experiment challenge different parts of a fully classical picture. Classical electromagnetic waves successfully describe propagation, interference and diffraction, while classical particles follow trajectories determined by forces. The difficulty is combining that picture with the observed exchange of energy between radiation and matter, the equilibrium distribution of radiation, and electron scattering. The three experiments expose the roles of discrete energy exchange and coherent matter waves.
In a photoelectric effect experiment, monochromatic light illuminates a metal cathode in vacuum and a second electrode collects emitted Electrons. Varying the collecting voltage measures a photocurrent; reversing it until collection ceases determines the stopping potential. The observations distinguish two controls: at fixed frequency above threshold, increasing light intensity increases the emission rate, whereas the largest emitted kinetic energy is determined mainly by frequency. There is a material-dependent photoelectric threshold frequency, and emission above threshold does not require the long charging-up delay predicted by a simple picture of gradual classical energy accumulation at low intensity.
A classical wave carries continuously distributed energy, with intensity proportional to squared field amplitude. On a fully classical absorption picture, increasing intensity would be expected to increase the energy delivered to an electron, and sufficiently long exposure could accumulate the escape energy even below the observed threshold. It does not naturally produce the measured universal straight-line relation between stopping potential and light frequency. In 1905, Albert Einstein instead treated light-energy transfer as localized quanta. His argument distinguished the fastest escaping Electrons from electrons losing energy before escape.[ref]
On a Heuristic Point of View Concerning the Production and Transformation of Light by Albert Einstein. §8, printed pp. 193–196, energy balance and frequency versus intensity predictions
In the single-photon regime, conservation of energy gives the Einstein photoelectric equationwhere is the surface work function. The photon supplies energy ; the escape cost is paid first, and the remainder sets the upper electron-energy edge. Increasing intensity at fixed frequency increases the number of available photons, so it raises current without raising this edge. Below , one photon cannot pay the escape cost. In an actual measurement, stable surface preparation, suppression of unwanted higher-frequency light, and the photoelectric contact-potential correction are needed to test the slope reliably. Robert Andrews Millikan's experiment used selected mercury spectral lines, freshly exposed metal surfaces and an electrometer to make such a quantitative test.[ref]
A Direct Photoelectric Determination of Planck's h by Robert Andrews Millikan. §§2–4, printed pp. 361–375, apparatus and stopping-potential measurements
The interpretation is for weak single-photon illumination; multiphoton photoemission at sufficiently intense fields is a different regime.Black-body radiation tests equilibrium physics rather than the escape of individual electrons. A small aperture in an isothermal absorbing cavity approximates an ideal blackbody: radiation entering the hole undergoes repeated interactions with the walls, and the equilibrium spectrum depends on temperature rather than wall material. A spectrally resolving detector outside the aperture measures how emitted power varies with frequency or wavelength. Experimentally the spectrum has a finite peak, is strongly suppressed at short wavelengths, shifts toward shorter wavelengths when the cavity is heated, and has integrated emission proportional to .
For a large cavity, the electromagnetic mode density in a box, including two independent transverse polarizations, is per volume per unit frequency. The classical equipartition theorem assigns mean energy to each mode, leading to the Rayleigh-Jeans lawThis agrees at low frequencies but diverges as frequency increases; integrating it over all frequencies gives infinite energy density at any nonzero temperature. This is the ultraviolet catastrophe, a failure of classical equipartition applied to the electromagnetic modes.
Max Planck's essential modification was that energy at a frequency is exchanged in units . In a modern oscillator description, the thermal excitation levels are , . Using the Boltzmann distribution and summing a geometric series givesMultiplying by the mode density yields Planck's law for the spectral energy density,When , expansion of the denominator recovers the classical law. When , the large excitation cost suppresses occupancy exponentially, removing the divergence. Its integral gives the Stefan–Boltzmann law, while its peak gives Wien's displacement law. Thus quantization repairs the spectral shape, total emission and temperature dependence together. The displayed thermal energy excludes the oscillator's temperature-independent zero-point energy.
The Davisson–Germer experiment supplies the complementary evidence that matter cannot always be treated as classical particles with definite scattering trajectories. In 1927, Clinton J. Davisson and Lester Halbert Germer sent a narrow, accelerated electron beam normally onto a single nickel crystal in vacuum. A movable collector measured the current of scattered Electrons as direction and accelerating voltage were varied; a retarding potential selected electrons retaining approximately the incident energy. Sharp angular beams depended on crystal orientation and beam energy, with a prominent feature near and detector colatitude . These are scattering directions and currents, not photographs of electron paths.[ref]
Diffraction of Electrons by a Crystal of Nickel by C. Davisson and L. H. Germer. Printed pp. 707–710, apparatus; pp. 715–719, voltage and angular scans
The de Broglie wavelength predictsAt , this gives , comparable to atomic spacings. A crystalline arrangement supplies regularly spaced scattering sites, so scattered probability amplitudes can add constructively in selected directions. For a suitable family of crystal planes, Bragg's law expresses the condition as , with measured relative to those planes. The detector colatitude is not automatically this angle. The measured angular structure and its variation with electron momentum are described by electron diffraction with the de Broglie wavelength. A classical point-particle deflection model has no phase wavelength and does not supply that interference condition.
The common quantum account preserves the successes of wave propagation and particle detection while changing what is quantized. Photons exchange energy in frequency-dependent units; a thermal distribution of those excitations gives the blackbody spectrum. Electrons have a wavefunction whose amplitudes interfere on scattering from a crystal, while detection transfers localized charge. The Born rule turns squared amplitudes into event probabilities. These results invalidate a fully classical description of matter and radiation; the photoelectric energy law alone does not establish every property of a quantized electromagnetic field, but the three phenomena together provide complementary evidence for the quantum description.
Past exam of the physics B course of the University of Cambridge 2022 Paper 2 Section A A5 Solution 2026-10-18
Let be the upper- and lower-level populations and their degeneracy factors. At thermal equilibrium, the Boltzmann distribution givesNo degeneracy factors are supplied, so the numerical answers use equal degeneracy factors. Stating the ratio as upper population divided by lower population removes an otherwise arbitrary inversion.
(a) At ,The two populations are nearly equal because the level separation is much smaller than the thermal energy .
Each independent cavity mode is a quantum harmonic oscillator of angular frequency . Its occupation numbers represent the numbers of photons in that mode. At thermal equilibrium, photons can be absorbed and emitted by the walls, so their number is not conserved and the photon chemical potential is zero. The Boltzmann distribution of the oscillator excitations then givesThe expression supplied in the paper is the thermal excitation energy. The oscillator's temperature-independent zero-point energy is excluded from the emitted thermal radiation.
Putting and into the mode count from (a) gives the number of modes per unit cavity volume:Multiplying by the mean thermal energy in each mode yields Planck's law in the angular-frequency convention:The two photon polarizations are already included in the density of states; no further factor of two is needed. has units , whereas has units .
In the nondegenerate conduction band, the Fermi-Dirac distribution reduces to its Boltzmann distribution tail. ThusHere the substitution leaves . For electron holes use the empty-state probability , not the conduction-band Boltzmann factor. This givesThe chemical potential cancels in the product. With ,This semiconductor mass-action law holds in thermal equilibrium for nondegenerate carriers, including a doped semiconductor. Only in an intrinsic semiconductor must . The factors are the effective density of states; the factor in the final expression follows from the two spin factors already included in (a).
Two stabilization mechanisms. Steric stabilization coats each colloid with adsorbed or grafted polymer layers. Bringing two particles close overlaps or compresses those layers, increasing their free energy through loss of chain conformations and, in a suitable solvent, increased local osmotic pressure. The resulting repulsion can keep the cores apart. A well-solvated nonionic coating can remain effective when added salt would screen electrostatic forces. Coatings can fail through desorption, poor solvent conditions or bridging, so simply adding arbitrary free polymer does not guarantee stabilization.
Charge stabilization of colloids instead uses similarly charged surfaces and their diffuse electric double layers. Their approach costs electrostatic and ionic free energy. In DLVO theory, that repulsion competes with attractive Van der Waals forces. It is particularly sensitive to salt concentration, counterion valence and surface ionization.
Bjerrum length. The standard Bjerrum length is the separation at which the Coulomb interaction energy of two elementary charges equals thermal energy:At and , this isIt compares ionic electrostatic coupling with thermal agitation. For ions of signed valences , . The standard reference length uses , not the whole colloid charge: assigning a colloid charge does not change the solvent's tabulated .
Screening and the printed normalization. In a symmetric electrolyte, is the ionic valence magnitude, the elementary electric charge, the bulk number density of each ionic species, the vacuum permittivity, the solvent's relative permittivity, the Boltzmann constant and absolute temperature. Mobile ions rearrange around a charged surface; the Debye–Hückel screening length sets the range of the resulting weak potential.
There is an SI normalization error in the original PDF. Combining the Boltzmann distribution with the SI Poisson equation and linearizing at givesThe extra in the PDF denominator is inconsistent with those SI charge, permittivity and density conventions. Keeping the printed algebra would make its screening length times the SI value at the same ion density. No numerical screening length is required here, and the qualitative dependence is the same in either normalization. Added salt shortens the range of repulsion, allowing the attractive potential to capture particles more readily.
Interaction-potential sketches. Let be the surface separation between two spheres of radius . A useful schematic DLVO theory potential has the formaway from the microscopic contact region. Here is a Hamaker constant; excluded-core repulsion and molecular details regularize contact. The exponential is the double-layer repulsion and the inverse-gap term the short-gap Van der Waals force contribution. A fixed illustrates the changing screening range; actual charge regulation can change the repulsive amplitude as well.
At low salt there is a high positive barrier between a deep primary minimum near contact and the dispersed state at . A shallow secondary minimum can occur outside the barrier and support weak reversible association. Increasing salt narrows the repulsive range and lowers the barrier. Thermally activated primary aggregation becomes appreciable when the barrier is only a few ; the idealized barrier-free condition defines the fast-aggregation threshold associated with the critical coagulation concentration. Above that threshold, collisions can result in rapid capture in the primary minimum.
Original schematic DLVO potentials as screening increases
. Illustrative dimensionless amplitudes show the barrier and outer attractive minimum; the near-contact primary well extends below the plotted range. These curves do not determine a material-specific coagulation concentration. Details.Aggregate structures. Well above the critical coagulation concentration, the sticking probability is close to one. In diffusion-limited cluster aggregation, the first encounter attaches particles or clusters at accessible outer branches before they can explore many alternative configurations. The result is an open, tenuous structure. Typical ideal three-dimensional cluster models have mass fractal dimension .
Near the threshold on its lower-salt, slow-aggregation side, a remaining barrier makes most encounters unsuccessful. Reaction-limited cluster aggregation then permits repeated approaches and orientations before attachment, commonly giving denser clusters with . Since particle count scales as , the larger exponent means more particles at a given large cluster size. This explanation does not require already formed bonds to rearrange: unsuccessful encounters themselves alter which configurations eventually bind.
The side of the threshold matters. At the ideal barrier-free threshold itself, or just above it, aggregation can already be diffusion limited; proximity to the critical coagulation concentration alone does not universally imply a denser reaction-limited structure. The quoted dimensions are typical of irreversible approximately isotropic cluster models, not exact values for every colloid. Strong bond rearrangement or anisotropic attractions can change this comparison.
Diffusion and mobility. For a dilute isolated sphere in a Newtonian fluid, Stokes's law gives the drag magnitude , where is the dynamic viscosity and is the hydrodynamic radius. The mechanical mobility is therefore ; the translational hydrodynamic mobility matrix is .
To relate mobility to diffusion, put the particles in a weak external potential energy . Their drift speed is . For number density , the sum of drift and Fick's first law fluxes isAt thermal equilibrium, the Boltzmann distribution gives , and the net flux is zero. Substituting into yields . Thus the Stokes–Einstein relation isHere is the Boltzmann constant and is absolute temperature. The assumptions include a no-slip approximately spherical particle, a continuum fluid, a small particle Reynolds number, and negligible hydrodynamic interactions with other particles or boundaries.
Gravitational sedimentation. The buoyant force must be included, since the mass of displaced water is comparable to the protein mass. Using givesso the buoyant mass in the stated spherical model isThe drag coefficient is . At terminal speed, , soIgnoring buoyancy would give and would not use the supplied water density. This calculation treats the stated radius as both the hydrodynamic radius and the radius determining displaced volume; a real hydrated protein can require a separately measured partial specific volume.
Electrical drift. In the specified simple electrophoresis model, terminal force balance is . Thereforewhere is the electrophoretic mobility and the elementary electric charge. For the given positive beta-lactoglobulin charge,in the direction of the electric field. This exceeds the gravitational sedimentation speed by about .
Separation time. The two populations have equal drag coefficients because their radii are equal. Their difference in drift speed is therefore set by one elementary charge:Starting with coincident band centres, their separation is . HenceAt that time the original band has travelled and the mutant . Their masses do not enter this ideal electrical force balance: equal-radius particles with different masses but the same charge would have equal electrophoretic mobility in this model.
Practical discrimination. A one-charge difference is enough for the stipulated separation, so the method is sensitive to mutations that change effective charge or friction. It cannot distinguish every mutation: substitutions that preserve charge and hydrodynamic size need not separate. Buffer pH changes protein ionization, and realistic electrophoresis also involves the ionic atmosphere, electro-osmosis, walls or gel interactions, and finite band widths.
For example, the Stokes–Einstein relation at gives . For an initially narrow band, diffusive broadening of electrophoretic bands givesat the calculated separation time. Thus the centres are about diffusion standard deviations apart, rather than forming infinitely sharp bands. The stated centre-separation criterion is achievable in the model, but actual resolution also depends on the loading width and other dispersion mechanisms.
Equivalent centrifugal acceleration. For the original protein to attain its electrical drift speed by sedimentation, its buoyant centrifugal force must equal :ConsequentlyThis is the acceleration at the protein's position in the rotating solution; no rotation rate can be assigned without a centrifuge radius. If the intended comparison is instead the relative separation speed of the two bands, use , since their displaced volumes are equal. Matching then gives . In that separation experiment the heavier original protein moves faster centrifugally, whereas the more highly charged mutant moves faster electrically.
Stabilization and screening. Charge stabilization of colloids means suppressing aggregation through repulsion between similarly charged particles and their electric double layers. In DLVO theory, this repulsion competes with attractive Van der Waals forces. A substantial repulsive barrier compared with thermal energy can make aggregation slow, even when the dispersed state is only metastable.
The Debye–Hückel screening length is the characteristic range over which a weak electric potential is attenuated by rearrangement of mobile ions. It measures the thickness of a diffuse screening cloud, not a molecular diameter. For a plane, a weak potential decays as into the bulk.
Derivation and the source convention. Put a planar interface at , with electrolyte in , bulk potential zero, and absolute permittivity . For a symmetric electrolyte, let be the bulk number density of each ionic species. The Boltzmann distribution givesso the mobile charge density isSubstitution into the SI Poisson equation, , gives the Poisson-Boltzmann equationFor , linearize the hyperbolic sine. The Debye–Hückel approximation is thenHere is the ionic valence magnitude, the elementary electric charge, the Boltzmann constant, absolute temperature, the vacuum permittivity, and the solvent's relative permittivity. For several ionic species, the numerator is replaced by .
The original PDF includes an additional in the denominator. That factor does not follow from SI Poisson equation with number densities and the stated permittivities. The Bjerrum length provides a useful check: and the consistent result is . A Gaussian-unit convention moves factors of together with the charge and permittivity conventions; it does not justify inserting this extra factor while retaining all the given SI quantities. Both numerical interpretations are reported below rather than silently changing the source.
Conditions favoring stability. Increasing the surface-potential or surface-charge magnitude usually strengthens the electrostatic barrier. Lower ionic strength increases and generally makes repulsion longer ranged; added salt and especially multivalent counterions shorten it and can promote aggregation. Suitable pH can keep an ionizable surface charged, while conditions near an isoelectric state weaken charge repulsion. The solvent-dependent Van der Waals forces, charge regulation and particle geometry also affect the barrier, so a long screening length is not by itself sufficient. At fixed density and valence, the linear formula gives , but actual temperature changes can also alter the permittivity and surface chemistry.
Surface charge at small potential. Take the usual one-sided planar-interface model, with negligible electric displacement on the nonaqueous side. The solution decaying into the solution isThe electric field is . The electrostatic interface boundary conditions then give the surface charge densityOne can also derive it by integrating the diffuse charge density:Thus the diffuse layer neutralizes the surface charge. This is the planar Debye-Hückel double layer. If instead the object is an isolated sheet wetted by identical electrolyte on both sides, each side screens half its total charge and . The one-sided assumption is the conventional local model for the exterior of a large charged colloid; it must be stated because the question does not specify the material on the other side.
Numerical ion density. For , , and , the consistent SI result isThis is for each ion species, and hence also the salt concentration for a monovalent salt. The combined number density of both signs is .
Literal substitution into the formula printed in the PDF instead givesThese values are distinct consequences of the source's extra factor; they cannot both describe the same physical screening length in SI with the same definition of .
Surface potential and validity. The requested linear estimate in the one-sided model isHowever, the thermal voltage is , so . Thus the small-potential approximation is not self-consistent for the supplied surface charge. The boxed value is its formal extrapolation, not a reliable prediction of the actual surface potential.
For a valid nonlinear comparison within the ideal one-sided planar Poisson-Boltzmann equation, multiply the differential equation by and use zero potential and field in the bulk. This givesUsing the surface boundary condition yields the Grahame equation and its inverse:With the SI screening length, the latter gives . This is a nonlinear mean-field estimate under explicit assumptions, not a unique experimentally determined potential: compact interfacial layers, finite ion size and surface chemistry were not supplied. The source's normalization problem and its use of a linear formula far outside the small-potential regime are separate issues.
The gap is not a fixed mechanical separation. Thermal fluctuations of the wall compete with drift towards the microtubule under the opposing force. A monomer can be incorporated only after the gap reaches its length. The Smoluchowski equation describes this overdamped drift and diffusion of gap probability density.
For gap potential energy , the equation and its probability current areThe drift mobility is , the overdamped consequence of the fluctuation-dissipation relation for a Langevin particle. Equivalently, this coefficient is fixed by requiring the zero-current solution to be the Boltzmann distribution . Solve this equation with the appropriate exclusion, incorporation and probability-normalization conditions. The steady flux through the incorporation threshold gives the addition rate ; the elongation speed is .
There is a regime distinction in the printed problem. The absorbing boundary imposed in part (c) means instantaneous incorporation once a gap opens, and leads to the diffusion-limited Brownian ratchet with constant load. A genuinely reaction-limited polymerization Brownian ratchet instead assumes fast gap equilibration followed by a finite chemical addition rate, giving an exponential gating factor multiplying that chemical rate. The equations requested in the subsequent parts specify the former model, which is the one solved here.
In the steady state, conservation of probability requires , so is constant. The sign is positive because increasing gap reaches the incorporation boundary, whereas the deterministic drift points towards smaller gap. ThusAn integrating factor givesSubstitution makes the check particularly transparent:so . The constant offset is necessary for nonzero transport; a pure Boltzmann distribution would have and could not describe a steady succession of addition events. The limit is taken after applying the boundary conditions, avoiding the apparent singularity of the displayed parametrization.
Each addition starts a new statistically identical waiting episode at zero gap. Thus the addition rate is the reciprocal of a mean first-passage time, not the reciprocal of the mean gap:This can also be derived without the steady density. If is the mean time to reach starting at gap , its backward Smoluchowski equation isThe first boundary is reflecting and the second absorbing. An integrating factor gives , whenceAt weak force, is the time for a freely diffusing wall to move a monomer length, with reflection at the tip. At strong force, opening the gap requires work , with Boltzmann distribution suppression . The drift establishes a near-tip thermal length and a diffusion time ; consequentlyThe exponentially long wait explains why the growth slows. There is no additional chemical waiting time in the imposed absorbing-threshold model; such a time would be needed to describe the separate reaction-limited polymerization Brownian ratchet regime.
Let be the permittivity, , the elementary charge, and the bulk salt formula-unit number density. The Boltzmann distribution givesConsequently the exterior Poisson-Boltzmann equation isFor small , meaning , linearize the exponentials. The Debye–Hückel approximation givesThis is also : the divalent cation contributes and the two monovalent anions contribute . In terms of molar salt concentration in , replace by ; if is in , use . The molar ionic strength is in the same concentration units.
The boundary conditions are and, by Gauss's law,Here the surface charge is uniform and the spherically symmetric interior field is zero. Set ; the radial equation reduces to . Decay excludes the growing exponential, so write . Then , givingIt solves the linearized Poisson-Boltzmann equation, not the full nonlinear equation at finite . The radial ion profiles, consistently to first order, areThe exponential Boltzmann distribution formulas above express the full mean-field relation, but substituting a linearized potential into them is accurate only to the retained order. A useful electroneutrality check isThe result is the Debye-Hückel potential of a charged sphere.
Past exam of the theoretical physics I course of the University of Cambridge 2022 3 c Solution 2026-10-18
The self-consistency equation requires that the mean spin computed using the single-site Boltzmann distribution equals the spin used to form the effective field. With ,ThusEquivalently, differentiating part (b) gives , so stationarity of the Helmholtz free energy in the mean-field approximation is exactly this condition. Among multiple stationary points one must select the stable minimum.

