Past exam of the quantum condensed matter course of the University of Cambridge / 2004 / Section B

This is the Joule-Thomson coefficient, ${\mu }_{JT}=(\partial T/\partial P{)}_H$, describing a temperature change during an isenthalpic pressure change. Here $H$ is enthalpy, $C_P=(\partial H/\partial T{)}_P$ is the heat capacity at constant pressure, and $V$ is volume, all for the same chosen amount of substance. Starting with $dH=TdS+VdP$ and using the Gibbs free-energy Maxwell relation $(\partial S/\partial P{)}_T=-(\partial V/\partial T{)}_P$ givesSetting $dH=0$ provesIn a steady insulated throttle or porous plug, negligible kinetic- and potential-energy changes make the upstream and downstream enthalpies equal. A positive coefficient gives cooling on a pressure decrease; a negative one gives warming. For an ideal gas, $V\propto T$ at fixed $P$, so the coefficient is zero. Real-gas interactions permit cooling and an inversion curve, making the effect useful in gas refrigeration and liquefaction.

The measurement of the Joule-Thomson effect with a porous plug compares pressures and thermometers on the two sides of an insulated flow restriction. Suppressing external heat exchange and separating the readings from high-speed jets are part of making the enthalpy argument applicable; an arbitrary adiabatic expansion need not be isenthalpic.

The Clapeyron equation gives the slope of a two-phase phase coexistence curve. Let $s_l,s_v$ and $v_l,v_v$ be entropy and volume per molecule, or consistently per mole. Equality of the two chemical potentials and $d\mu =-sdT+vdP$ implyAt reversible coexistence the latent heat in the same amount convention is $\mathcal{L}=T(s_v-s_l)$. ThereforeThe relation assumes thermodynamic equilibrium between two bulk phases of a pure substance, neglecting curvature and other work terms. For vaporization both latent heat and volume change are positive, giving a positive vapor-pressure slope. If the vapor is approximately ideal and its volume dominates, the ideal-vapor Clausius-Clapeyron approximation gives $d\ln P/dT\simeq \mathcal{L}/(k_B{T}^2)$ with latent heat per molecule.

Experimentally, a sealed two-phase sample in a temperature-controlled bath supplies the coexistence pressure as temperature changes. Independent calorimetry and phase-density measurements supply $\mathcal{L}$ and $\Delta v$, allowing the pressure slope to test the equation. The formula connects those distinct measurements and is a practical route to latent heats.

This relates an thermodynamic equilibrium variance to the local stiffness of an appropriate thermodynamic free energy. At fixed bath temperature, suppose the effective thermodynamic free energy $A(x)$ includes the constraints and the measure for a chosen coordinate. Its thermodynamic equilibrium probability density function is proportional to $e^{-A(x)/(k_{B}T)}$. Near a stable minimum $x_0$, writeThe resulting normal distribution gives the Gaussian fluctuation approximationThis is exact for a quadratic thermodynamic free energy with the stated flat coordinate measure; in general it is a small-fluctuation result. A smaller curvature means a softer restoring response and larger fluctuations. Near vanishing curvature, higher-order terms become important, so the quadratic approximation cannot alone predict an actual infinite variance.

For example optical trap Langevin calibration uses the Brownian displacement of a trapped bead: $A=\kappa (x-x_0{)}^2/2$ gives $\kappa =k_{B}T/⟨\Delta x^2⟩$. A camera or position detector records the fluctuations. Finite exposure averages rapid motion and can bias the measured variance; the measurement protocol matters as well as the thermodynamic equilibrium identity.

Entropy is a thermodynamic state function. For a reversible heat transfer, $dS=\delta Q_{\mathrm{rev}}/T$; the Clausius inequality generalizes this to irreversible processes. The combined entropy of a system and its surroundings does not decrease. A subsystem can lose entropy by exporting heat or matter, so the second-law statement must specify the whole isolated combination. In a simple compressible system,which identifies temperature, pressure and chemical potential as derivatives of the energy representation of the state function. Thermodynamic equilibrium maximizes entropy under fixed total energy, volume and particle number. A heat reservoir instead leads to minimizing the Helmholtz free energy at fixed $T,V,N$, or the Gibbs free energy at fixed $T,P,N$.

Statistical mechanics explains the state count. In a microcanonical ensemble, equally probable compatible microstates give Boltzmann's entropy formula, $S=k_B\ln \Omega$. With general discrete probabilities, the Gibbs entropy isThe microcanonical formula follows by setting every nonzero probability to $1/\Omega$. For a canonical ensemble, $p_j=e^{-\beta E_j}/Z$, soThis turns microscopic energy levels and their populations into a measurable thermodynamic quantity. Classical phase-space counting needs a consistent microscopic normalization and indistinguishability convention; quantum state counting supplies that normalization. Independent systems have multiplicative state counts and therefore additive entropies.

For an ideal gas freely expanding from volume $V$ to $2V$ in an insulated enclosure, energy remains fixed while each particle gains twice the accessible position volume. The state count increases by $2^N$, giving $\boxed{\Delta S=N{k}_B\ln 2}$. The actual irreversible process transfers no heat. A reversible isothermal comparison path transfers heat $N{k}_{B}T\ln 2$ and computes the same entropy change because the initial and final thermodynamic equilibrium states are the same.

Calorimetry supplies another connection to experiment: at fixed pressure and within one phase, $S(T)-S(0)={\int }_0^T{C}_P(T^{\prime })d{T}^{\prime }/T^{\prime }$, with latent-heat contributions $\mathcal{L}/T$ at first-order transitions. The third law of thermodynamics fixes $S(0)=0$ for an ideal perfect crystal with a unique ground state. Degeneracy or frozen disorder can produce residual entropy. Entropy thus links heat-capacity measurements, phase thermodynamic equilibrium and the number of accessible microscopic configurations.

Charge carrier mobility measures weak-field drift speed per electric field. For electrons and electron holes,Both mobilities are positive, with SI units ${\mathrm{m}}^2{\mathrm{V}}^{-1}{\mathrm{s}}^{-1}$; the opposite drift signs reflect the opposite carrier charges. In a simple isotropic relaxation-time model, electron mobility is ${\mu }_e=e{\tau }_e/m_e^{\ast }$ and hole mobility is ${\mu }_h=e{\tau }_h/m_h^{\ast }$. These are momentum relaxation times, not the minority carrier lifetime for electron-hole recombination.

Scattering by phonons, ionized impurities and defects limits mobility. Increasing phonon populations commonly lowers mobility at high temperature; ionized-impurity scattering can dominate at low temperature and high semiconductor doping. Approximate addition of independent inverse relaxation times is the Matthiessen's rule. At sufficiently strong field, velocity saturation invalidates the constant-mobility drift law.

The Hall effect provides a measurement: a current-carrying bar in a perpendicular magnetic field develops a transverse voltage. In a one-carrier model $|R_H|=1/(en)$ and $\mu =\sigma |R_H|$, combining the transverse voltage with longitudinal electrical conductivity. Multiple carrier types and scattering-dependent Hall factors require a more detailed interpretation.

Generation increases the mobile electron or hole populations; interband excitation creates an electron-hole pair. Thermal excitation and absorbed photons are important sources, and impact ionization can multiply carriers in a strong field. Ordinary single-photon interband absorption needs enough photon energy to bridge the band gap, with the required momentum balance.

Electron-hole recombination removes a pair. Radiative electron-hole recombination emits a photon, with simple rate $Bnp$; trap-assisted electron-hole recombination uses localized defect levels and transfers energy to the lattice; Auger recombination transfers the electron-hole recombination energy to another carrier. The last process becomes especially important at high injection because its rate contains products such as $n^{2}p$ and $n{p}^2$. The detailed band structure and available defects determine which channel dominates.

At thermal thermodynamic equilibrium, generation and electron-hole recombination continue at equal rates. For the simple radiative model the net electron-hole recombination rate is $B(np-n_i^2)$, enforcing the semiconductor mass-action law. Under weak excitation with the majority density nearly fixed, an excess minority density often decays as $\Delta n(t)=\Delta n(0)e^{-t/\tau }$, defining its minority carrier lifetime.

A short light pulse followed by time-resolved electrical conductivity or luminescence measures the relaxation. Spatial diffusion, trapping and instrumental response must be separated from electron-hole recombination before identifying a single fitted decay constant with the intrinsic lifetime. These processes control photodetector response and light-emitting-device efficiency.

An n-channel MOSFET has two heavily n-doped source and drain regions in a p-type body, with an insulated gate above the intervening surface. A positive gate voltage first depletes surface electron holes and then induces an electron semiconductor inversion layer. Above threshold $V_T$ this layer connects source to drain. Gate voltage controls the channel charge through the oxide capacitance, while the insulating gate permits a very small steady gate current.

For the long-channel MOSFET current law, let $C_{\mathrm{ox}}$ be oxide capacitance per area, $W,L$ channel width and length, and use constant mobility ${\mu }_n$. In the gradual-channel approximation,At larger drain voltage the ideal channel pinches off near the drain and the current saturates atCarriers still flow through the pinch-off region; pinch-off does not mean zero drain current. These formulas neglect channel-length modulation, short-channel effects and velocity saturation. A p-channel device reverses the carrier type and operating polarities. Gate control makes MOSFETs useful as electronic switches and amplifiers.

Exchange interactions arise from quantum electronic motion, Coulomb interactions and fermionic antisymmetry. A localized-spin description can be written $H={\sum }_{i<j}{J}_{ij}{\mathbf{S}}_i\cdot {\mathbf{S}}_j$. In this explicit plus-sign convention $J<0$ favors parallel spins and $J>0$ favors antiparallel spins; many texts put a minus sign into the Hamiltonian and reverse that convention.

Direct exchange involves overlapping orbitals and their Coulomb exchange matrix elements. The Pauli exclusion principle correlates spin symmetry with spatial symmetry, changing the electronic energy. Orbital occupation and competing kinetic processes determine which spin state is favored; the preference is not universally ferromagnetic.

Superexchange couples moments through virtual hopping, often via a nonmagnetic ligand. For two half-filled orbitals in the simple repulsive one-band model, the antiferromagnetic coupling is $J\simeq 4|t{|}^2/U$: virtual double occupation lowers the antiparallel-spin state more effectively. Orbital geometry and intermediate-state interactions can change the sign in other configurations. Real charge transport can remain insulating while this magnetic coupling acts.

Double exchange instead uses actual carrier motion between mixed-valence sites. Local Hund's coupling ties the mobile electron's spin to a core moment. Parallel neighboring cores allow a larger effective hopping amplitude and a lower carrier kinetic energy, favoring ferromagnetism. The original model explicitly connected conduction and magnetic order in manganese perovskites.^[ref]

Conduction-electron-mediated exchange couples localized moments through a metal's electronic spin response. Its strength and sign depend on separation and the Fermi surface; in a simple three-dimensional asymptotic model the range factor oscillates as $\cos (2k_{F}r)/r^3$. The original nuclear-moment calculation was motivated by resonance-line broadening in silver.^[ref] In an itinerant metal, an alternative description compares the kinetic-energy cost of unequal spin populations with the exchange-energy gain; the Stoner criterion expresses when spontaneous polarization is favorable.

The resulting order also depends on the lattice and competing couplings. In ferromagnetism, moments align to give a nonzero moment within a domain. In antiferromagnetism, opposing sublattices cancel their moments. In ferrimagnetism, oppositely ordered sublattices have unequal moments and leave a net one. A bulk zero magnetization alone cannot distinguish antiferromagnetic order from a disordered state or canceling magnetic domains.

The manganese monoxide neutron diffraction experiment makes that distinction experimentally. A monochromatic neutron beam scatters from powdered material, and a counter records angular intensity. Comparing the same compound at room temperature and $80\mathrm{K}$ reveals additional low-temperature magnetic reflections, indexed by a larger magnetic unit cell, while nuclear reflections persist. That spatial periodicity is evidence of alternating order even though the net moment cancels.^[ref]