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The inspected cover literally names Applications of Quantum Mechanics, Lent Term 2017, University of Cambridge Part II Mathematical Tripos, by David Tong. Chapter4, phonons: www.damtp.cam.ac.uk/user/tong/aqm/aqmfour.pdf. Section4.1.1 is printedpp.103–105;§4.1.4 beginsprintedp.110. Keep this archived work distinct from the existing Topics in Quantum Mechanics by David Tong, whose current PDF has a different title and chapter layout. No claim that these2017 notes were supplied with the2016 exam is made.

The spin-one-half low-energy expansion of the Dirac equation includes this local correction in a static potential energy V. For $V=-Z{e}^2/(4\pi {ϵ}_{0}r)$, ${\nabla }^{2}V=Z{e}^2{\delta }^{(3)}(\mathbf{r})/{ϵ}_0$, so the correction is positive and probes the wavefunction at the origin. In point-Coulomb hydrogen atom states it contributes only to S waves at leading nonrelativistic order. It is part of fine structure, distinct from the radiative Lamb shift. ^[ref]

The WKB approximation, also called JWKB, describes a short local de Broglie wavelength in a slowly varying potential energy. For $p(x)=\sqrt{2m[E-V(x)]}$ in a classically allowed region, its two local waves areThe phase follows the classical momentum; its amplitude varies to conserve probability current. In a forbidden region, putting $\kappa (x)=\sqrt{2m[V(x)-E]}$ gives $\psi \simeq {\kappa }^{-1/2}[C{e}^{{\int }^x\kappa /\hslash }+D{e}^{-{\int }^x\kappa /\hslash }]$, with boundary conditions selecting the physical combination.

The WKB validity condition is $\hslash |p^{\prime }|/p^2\ll 1$, with the analogous condition on $\kappa$. It fails at a turning point where $E=V$. For a simple turning point, locally linearizing V yields an Airy function; matching fixes the relative amplitudes and a $\pi /4$ phase. Two such turning points give the two-turning-point WKB quantization conditionFor an opaque barrier, the WKB tunnelling exponent instead givesThe factor two distinguishes probability from amplitude. Matching determines the prefactor; the exponential alone is not accurate near the barrier top. These formulas connect bound state energy eigenvalues and quantum tunnelling to classical actions. ^[ref]

For a point, stationary proton, the leading hydrogen fine structure comes from three order-$1/c^2$ contributions to the nonrelativistic electron Hamiltonian:These are the relativistic kinetic-energy correction, spin-orbit interaction and Darwin term. The spin-orbit coefficient includes the Thomas precession factor of one half; $⟨\mathbf{L}\cdot \mathbf{S}⟩={\hslash }^2[j(j+1)-l(l+1)-3/4]/2$. The Coulomb Darwin contribution is a positive contact term, relevant for S states. These corrections distinguish total angular momentum $j=l\pm 1/2$, while leaving magnetic substates degenerate without an external field.

Writing ${\alpha }_{\mathrm{fs}}=e^2/(4\pi {ϵ}_0\hslash c)$, the combined hydrogen fine-structure correction isThus the splitting is of order ${\alpha }_{\mathrm{fs}}^2$ times the principal binding energy. In the $n=2$ shell, $2S_{1/2}$ and $2P_{1/2}$ remain degenerate in this approximation, while $2P_{3/2}$ is higher by $m_e{c}^2{\alpha }_{\mathrm{fs}}^4/32$. The Lamb shift lifts the remaining S–P degeneracy; hyperfine structure is a separate nuclear-spin effect. Neither is part of the displayed correction. Nuclear recoil and finite nuclear size have also been neglected. ^[ref]

A single-mode coherent state is an annihilation operator eigenstate:Its photon statistics are Poisson distribution: $⟨n⟩=\mathrm{Var}n=|\alpha {|}^2$. For optical quadratures $X=(a+a^{†})/2$, $P=(a-a^{†})/(2i)$, one has $[X,P]=i/2$ and $\mathrm{Var}X=\mathrm{Var}P=1/4$. Its field mean oscillates classically while retaining vacuum fluctuations.^[ref][ref]

A classical mixture of coherent states has a nonnegative Glauber-Sudarshan representation. A nonclassical state of light cannot be represented that way. Examples are a squeezed vacuum state, with quadrature variances $e^{-2r}/4$ and $e^{2r}/4$, and a nonvacuum number state, with zero photon number variance. Noise below the vacuum level in one quadrature, sub-Poisson number noise, or photon antibunching can witness nonclassicality. For $|n⟩$, $g^{(2)}(0)=1-1/n<1$; coherent light has $g^{(2)}(0)=1$. Thermal light has excess noise but is a classical mixture: noncoherent does not by itself mean nonclassical.

Define $\hslash {\omega }_0=E_2-E_1$ and use radiation energy density $u(\omega )$ per unit angular frequency, excluding the zero-point contribution. The Angular-frequency Einstein coefficients give rates per atom: $B_{12}u({\omega }_0)$ for absorption, $B_{21}u({\omega }_0)$ for stimulated emission, and $A_{21}$ for spontaneous emission. Stimulated emission adds a photon to the stimulating mode; spontaneous emission persists with no incident photons.

In thermal equilibrium the Boltzmann distribution gives $N_2/N_1=e^{-\hslash {\omega }_0/(k_{\mathrm{B}}T)}$. Balancing up and down rates yieldsMatching the Planck law for every temperature fixesNo degeneracy factor is needed for these nondegenerate levels.^[ref]

For plates of large area $A$ and spacing $d$, the surviving low-frequency transverse electromagnetic mode has one polarization, $\mathbf{E}\parallel \hat{\mathbf{z}}$, and in-plane wavevector. Periodic in-plane counting givesMultiplying this single-polarization two-dimensional photon density of states by $\hslash \omega$ and the Bose-Einstein distribution produces the thermal radiation between parallel conducting plates:The same rate balance therefore givesThese $B$ coefficients refer to the radiation polarization in their respective environments: isotropic free-space $B$ must not automatically be equated to the coefficient for a specified $z$-polarized field.

For hydrogen, take the quantization axis along $z$, neglect spin-orbit coupling, and assume perfect plates, a wide in-plane region and an unmodified atomic wavefunction: $a_{\mathrm{B}}\ll d\ll c/{\omega }_0$, with negligible surface-induced mixing or shifts. The electric-dipole selection rules for hydrogen require $\Delta l=\pm 1$; the allowed $z$ field has $\Delta m_{\ell }=0$. Hence the polarization-selective spontaneous emission between conducting plates givesThe thin-cavity enhancement of a normal electric dipole applies: the $2p_0\to 1s$ dipole points along $z$ and couples to the enhanced mode density. For $m_{\ell }=\pm 1$, the transition dipoles lie in the $x$–$y$ plane and couple to none of these low-frequency modes: the electric-dipole decay rate is zero in the ideal model, so this channel's lifetime is infinite. Real finite, imperfect plates and additional decay or mixing channels limit the lifetime. The order-one orientation factor for the allowed transition does not change the requested lifetime scaling.

The central field approximation replaces the anisotropic many-electron environment by an average spherical potential, giving one-electron orbitals labelled by $n,l,m$. Screening changes the effective radial attraction and removes the pure Coulomb degeneracy between different $l$.

The Hartree method improves the potential self-consistently. For normalized occupied orbitals,Guess orbitals, construct their mean fields, solve the Hartree equations, and iterate to convergence. The $j\ne i$ sum excludes self-interaction in this product-state model. A spherical average can enforce the central-field specialization. A Hartree product state omits fermionic exchange and dynamical correlation; Hartree-Fock method adds antisymmetry and exchange through a Slater determinant. Converged orbital eigenvalues must not simply be added as the total energy, because that double counts pair interactions.^[ref]

A helium atom has two electrons bound to nuclear charge $+2e$. In the nonrelativistic fixed-nucleus approximation, using atomic units,The last term couples the electrons, so a product of independent hydrogenic orbitals is not an exact solution. The dominant ground configuration is $1s^2$. Its spatial wavefunction is symmetric, so Fermi antisymmetry requires the spin singletA triplet cannot put both electrons in the same $1s$ spatial orbital. Correlation changes the exact spatial function, including its dependence on $r_{12}$, while preserving this ground-state symmetry.

A useful helium variational effective charge takes normalized orbitals ${\varphi }_{\zeta }(\mathbf{r})=({\zeta }^3/\pi {)}^{1/2}{e}^{-\zeta r}$ for both electrons and multiplies their product by ${\chi }_{00}$. The energy in Hartree units isThe reduced effective charge expresses screening. Neglecting repulsion gives $-4E_h$, while its expectation in the unscreened $\zeta =2$ product gives $-2.75E_h$; optimizing the orbital improves that trial estimate. The exact ground energy is lower than the optimized product energy, since the product omits explicit electron correlation. This calculation keeps nuclear charge two in $H$; only the trial orbital parameter is varied.

For a singly excited helium state with distinct orthonormal orbitals $a=1s$ and $b=n\ell$, the spatial combinations areThe symmetric ${\Phi }_{+}$ pairs with the antisymmetric spin singlet, while antisymmetric ${\Phi }_{-}$ pairs with the symmetric spin triplet. With the same orbitals, their leading energies areHere $J_{ab}$ is the direct Coulomb integral and $K_{ab}$ is the exchange integral. The latter is positive for the Coulomb interaction, so the triplet is lower for this fixed-orbital comparison. singlet-triplet exchange splitting in helium arises from antisymmetry and spatial correlation in the Coulomb interaction, not from inserting a separate classical spin-spin force. Spin-singlet helium states are parahelium; spin-triplet helium states are orthohelium. The two spectra approximately form separate families because the leading electric dipole operator does not change total spin.^[ref]

The lowest $1s2s$ terms are ${}^3{S}_1$ and ${}^1{S}_0$, with the triplet lower. The $1s2p$ configuration gives ${}^3{P}_{0,1,2}^{\mathrm{o}}$ and ${}^1{P}_1^{\mathrm{o}}$, where the odd parity allows singlet $P$ to connect to the even-parity ground singlet by an electric dipole transition. Both $1s2s$ levels lack an allowed direct electric dipole decay to $1s^2$: the triplet is spin forbidden, and singlet $S\to S$ is forbidden by orbital angular momentum and parity. This explains helium metastability without implying an infinite lifetime once weaker radiative processes or collisions are allowed.

The observed first $1s2s$ excitation energies are approximately $19.82$ and $20.62\mathrm{eV}$ for the triplet and singlet, respectively. Higher singly excited Rydberg series approach the He II ground-state ionization threshold; doubly excited states above that threshold can autoionize and are not all stable bound excited levels.^[ref]

The WKB approximation describes a wave whose local wavelength changes slowly compared with one wavelength. For the one-dimensional stationary Schrödinger equation, put $p(x)=\sqrt{2m[E-V(x)]}$. In a classically allowed region,The phase is the classical action divided by $\hslash$. The amplitude varies as $p^{-1/2}$ so that a single travelling component has constant probability current. A useful local validity condition is $|\hslash p^{\prime }/p^2|\ll 1$.

For $V>E$, write $\kappa =\sqrt{2m(V-E)}/\hslash$. The wave instead has growing and decaying components proportional to ${\kappa }^{-1/2}\exp (\pm \int \kappa \mathrm{d}x)$. At a simple turning point, $p$ vanishes and neither local WKB expression is valid. Linearizing the potential gives an Airy-function solution that connects the two sides and supplies the turning-point phase shift. It is not legitimate to carry the divergent WKB amplitude straight through the turning point.^[ref]

A useful application is tunnelling through a smooth opaque barrier. With turning points $x_1,x_2$, the leading transmission probability isThe exponent is twice the forbidden-region action in units of $\hslash$, because transmission is a probability rather than a wave amplitude. For an ideal rectangular barrier of height $V_0>E$ and width $d$, the same leading exponential is $\exp [-2d\sqrt{2m(V_0-E)}/\hslash ]$; matching at the abrupt edges supplies an additional prefactor.

For a bound state between two smooth turning points, the related WKB quantization rule is ${\int }_{x_1}^{x_2}p\mathrm{d}x=(n+1/2)\pi \hslash$. In a harmonic potential the integral equals $\pi E/\omega$, recovering $E_n=(n+1/2)\hslash \omega$. This exact agreement of energies for the harmonic oscillator does not make WKB wavefunctions uniformly exact near its turning points.

Stimulated emission adds a photon to an already occupied radiation mode; spontaneous emission can occur when that mode initially contains no photons. In the electric-dipole approximation the atom-field interaction is $H_{\mathrm{int}}=-\mathbf{d}\cdot \mathbf{E}$. Quantizing the radiation field makes the emission matrix element into a mode with occupation $n$ proportional toThis photon occupation enhancement of emission makes the emission rate into that mode proportional to $n+1$: the part proportional to $n$ is stimulated and the remaining part is spontaneous. Absorption is proportional to $|⟨n-1|a|n⟩{|}^2=n$. The photon energy is the atomic energy difference, up to any specified recoil or line broadening.

The stimulated contribution preferentially populates the stimulating mode, including its propagation direction and polarization; it provides optical gain. Spontaneous photons populate the available modes according to the transition's dipole matrix elements and radiation environment. They are not universally isotropic. An excited bare atom with the field vacuum is not an eigenstate of the fully coupled Hamiltonian, which resolves the apparent paradox of a nominally stationary excited state radiating.^[ref]

For lower and upper levels 1 and 2, with radiation spectral energy density $u_{\nu }$ per unit ordinary frequency, the rates areThermal detailed balance with the Planck spectrum givesThe statistical weights $g_i$ here are level degeneracies, not Landé g-factors. A definition of $B$ multiplying intensity or angular-frequency density would change the normalization factors.

For a specified free-space electric-dipole transition, summing radiation modes givesAppropriate sums over final magnetic substates and averages over initial substates are needed for an unresolved degenerate level. The radiative lifetime is $1/A_{21}$ only when this is the sole decay channel. In a laser, net stimulated gain requires $N_2/g_2>N_1/g_1$, as well as sufficient gain to overcome cavity loss; population inversion alone does not specify the lasing threshold.

Fermi's golden rule converts a weak transition matrix element and the available density of final states into a transition rate. For a static perturbation $W$ and a continuum,When the matrix element is nearly constant on the energy shell, this becomes $(2\pi /\hslash )|W_{fi}{|}^2\rho (E_i)$. The energy delta function is to be integrated, rather than interpreted as a finite rate to one exactly resonant discrete level. The observation time must resolve a smooth final-state continuum while remaining short enough that first-order depletion is small. A periodically driven perturbation instead gives the corresponding absorption and emission energy shells.

For elastic scattering from a weak localized potential $W(\mathbf{r})$, use box-normalized free states $⟨\mathbf{r}|\mathbf{k}⟩={\mathcal{V}}^{-1/2}{e}^{i\mathbf{k}\cdot \mathbf{r}}$. ThenThe number of final states is $\mathcal{V}{k}_f^2\mathrm{d}{k}_f\mathrm{d}\Omega /(2\pi {)}^3$. With $E_f={\hslash }^2{k}_f^2/(2m)$, the density per energy and solid angle is $\mathcal{V}m{k}_f/[(2\pi {)}^3{\hslash }^2]$. Dividing the resulting golden-rule rate by the incident single-particle flux $j_i=\hslash k_i/(m\mathcal{V})$ givesThis is the golden-rule derivation of the Born cross-section. For the elastic problem $k_f=k_i$, so the first Born scattering amplitude and cross-section areThe box volume cancels, as a physical cross-section must. The minus sign is fixed by the outgoing-wave scattering convention; the golden-rule rate alone determines only the modulus.

For example, $W(r)=g{e}^{-\kappa r}/r$ has $\tilde{W}=4\pi g/(q^2+{\kappa }^2)$, hence $f_B=-2mg/[{\hslash }^2(q^2+{\kappa }^2)]$, with $q=2k\sin (\theta /2)$. Replacing the exact scattering state by the incident plane wave is the essential Born approximation. It can fail for strong scattering, low-energy resonances and situations requiring repeated scattering; a small perturbation and a suitable continuum are separate conditions.^[ref]

Spin-orbit coupling is a relativistic interaction between a particle's spin and its orbital angular momentum or, more generally, its motion through an electric field. A moving electron experiences a transformed magnetic field, which couples to its magnetic dipole moment. For an electron bound in a central electrostatic potential energy $U(r)$, the leading interaction, including the Thomas precession correction, isHere $\mathbf{L}$ is orbital angular momentum and $\mathbf{S}$ is spin. The factor of one-half relative to the simplest rest-field argument comes from Thomas precession of the accelerated electron frame.^[ref]

For example, in the hydrogen atom, the $2p$ states with total angular momentum $j=1/2$ and $j=3/2$ have different $\mathbf{L}\cdot \mathbf{S}$ eigenvalues. Their splitting is part of the atomic fine structure. The interaction redistributes and splits spin-dependent energies; it is not the same physical effect as the spin-independent convective magnetic force between charged filaments.

For small fixed positive $E$, the stated approximate curve has maxima atIts formal minima are zero at $\kappa a=n\pi$. The peak height is the $S$-wave unitarity limit, and the peaks narrow as $E/V_0$ decreases.

To identify the bound-state threshold, let the bound-state energy be $-\epsilon$ with $\epsilon >0$. The reduced radial wave is proportional to $\sin (Kr)$ inside and $e^{-\chi r}$ outside, with $K=\sqrt{2m(V_0-\epsilon )}/\hslash$ and $\chi =\sqrt{2m\epsilon }/\hslash$. Matching gives $K\cot (Ka)=-\chi$. As a new bound state emerges at $\epsilon \downarrow 0$,Thus the limiting peak locations coincide with the appearance of successive $S$-wave bound states. At the exact threshold the zero-energy radial solution is not square-integrable; a normalizable bound state appears just beyond it. Finite-energy maxima shift slightly from the zero-energy positions.

The formal minima require care because the assumption used in part d fails there. Retaining $ka$ in the exact matching condition gives the spherical square-well scattering lengthaway from a threshold. At $\kappa a=n\pi$, $a_s=a$, so the true low-energy S-wave scattering contribution is $4\pi a^2$, not zero. Genuine leading-order zeros of that contribution instead satisfy $\tan q=q$, for example $q\simeq 4.493409$ and $7.725252$. The original sketch compares the exact finite-energy $S$ wave with the requested approximation, making this nonuniformity visible. Dominance by the $S$ wave must be checked separately near a higher-partial-wave threshold. The scattering-length divergence and its bound-state interpretation are also derived in institutional lecture notes.^[ref]

Introductory course notes. Section 2: quantum states and harmonic oscillator and Section 4: quantum mechanics in three dimensions, including hydrogen. This is the introductory work, distinct from the advanced Topics in Quantum Mechanics by David Tong.

Displacing a one-dimensional quantum harmonic oscillator produces a linear force term and a scalar shift relative to the unshifted Hamiltonian. The scalar adds only a common phase. The linear term couples number states separated by one excitation. Arbitrary linear driving of the ground state creates a coherent state; a first-order expansion of that state contains only the vacuum and first excited state.^[ref]

Thomas precession is the kinematic rotation arising when the successive instantaneous rest frames of an accelerated particle are connected by noncollinear Lorentz boosts. Its contribution is needed in deriving the leading atomic spin-orbit coupling: for an electron in central potential energy $U(r)$, the corrected term is $H_{\mathrm{so}}=[2m_e^2{c}^{2}r{]}^{-1}(dU/dr)\mathbf{L}\cdot \mathbf{S}$. A rest-field argument alone gives twice this coefficient.^[ref]