Past exam of the atomic and laser physics course of the University of Oxford / 2021 / 1

The printed magnetic dipole moment uses dimensionless angular momentum operators: their physical counterparts are $\hslash \mathbf{L}$ and $\hslash \mathbf{S}$. Choose the magnetic field along $z$. Then the Zeeman energy is $H_Z={\mu }_{B}B(L_z+g_s{S}_z)$, whose characteristic size is ${\mu }_{B}B$. In LS coupling, treating this as a time-independent perturbation theory requires it to be much smaller than the relevant fine structure separation, rather than merely smaller than the Coulomb interaction energy.

For a concrete hydrogen atom estimate take the $2p_{1/2},2p_{3/2}$ pair. The hydrogen fine-structure correction iswhere ${\alpha }_{\mathrm{fs}}$ is the fine-structure constant, distinguished from the later potential coefficient. ThusConsequently a suitable weak-magnetic field condition for this pair isThere is no single threshold for every hydrogen energy level: the relevant fine structure separations decrease with $n$. The $1s$ energy level has no same-$n$ spin-orbit interaction partner, so it cannot itself define this comparison. This calculation neglects hyperfine structure; resolving that smaller scale requires an additional weak-magnetic field condition.

Within a fixed $L,S,J$ angular momentum multiplet, the component of $\mathbf{L}$ along $\mathbf{J}$ follows from $2\mathbf{L}\cdot \mathbf{J}={\mathbf{J}}^2+{\mathbf{L}}^2-{\mathbf{S}}^2$. The corresponding result for $\mathbf{S}$ follows by interchanging $L$ and $S$. For the quantum state $|LSJ{M}_J⟩$,These are dimensionless expectation values in the convention of part (a). Substituting into the first-order time-independent perturbation theory formula $\Delta E=⟨H_Z⟩$ givesFor $g_s=2$, the Landé g-factor becomesThe magnetic sublevels must first be diagonalized within a degenerate multiplet; choosing $M_J$ along the magnetic field already does this. For $J=0$ the displayed fraction is undefined, but all vector expectation values vanish and there is no first-order Zeeman splitting. A higher-order shift may remain.

Write $k=e^2/(4\pi {ϵ}_0)$ and retain the nuclear Coulomb potential. In spherical coordinates, the total potential energy iswhen $\beta =-\alpha /2$; $P_2(u)=(3u^2-1)/2$ is a Legendre polynomial. Treat the added term using quadratic anisotropic perturbation of hydrogen and degenerate perturbation theory in the $n=2$ hydrogen energy eigenbasis. It preserves parity and $m$, so it cannot mix $2s$ with $2p$, or distinct $2p$ magnetic sublevels.

For a hydrogen atom, the hydrogen radial second moment givesThe angular expectation values of ${\cos }^2\theta$ are $1/3$ for an $s$ orbital, $3/5$ for $p_0$, and $1/5$ for $p_{\pm 1}$, obtained by integrating the squared spherical harmonics. Therefore the five lowest spatial quantum states, counting statistical weight, have first-order energy levelsEach spatial quantum state has two electron spin states when spin-orbit coupling and the magnetic field are omitted. Thus these are five spatial states but only three distinct first-order energies; five distinct energies would be an incorrect reading. The accidental $2s,2p_{\pm 1}$ equality can be lifted at higher order. Quantitatively the added shifts must also be small compared with neighboring principal-shell gaps; $\alpha \ll k/a_0^3$ is an asymptotic condition, not a guarantee for arbitrary large $n$.

For general $\beta$, the $1s$ expectation value isIt does not cancel every order. At $\beta =-2\alpha$, $V_{\mathrm{ext}}=-2\alpha r^2{P}_2(\cos \theta )$ couples $1s$ to $d$ orbitals. For example its angular matrix element with $Y_{20}$ is $1/\sqrt{5}$, and the $3d$ radial matrix element is nonzero. The second-order nondegenerate perturbation theory sum has negative denominators, so this is a concrete nonzero higher-order contribution.

There is also a global limitation: for either negative $\beta$ above, $V(0,0,z)=-k/|z|+\beta z^2\to -\infty$. A localized wavepacket translated far along $z$ has fixed kinetic energy but arbitrarily negative potential energy, proving there is no true lowest energy level. The results describe local perturbative resonance poles, or a potential completed to a confining form far from the atomic nucleus. No globally exact ground-state cancellation exists for the potential as printed.

Neglect hyperfine structure, spin-orbit coupling and the diamagnetic term, and set $b={\mu }_{B}B$, $\epsilon =\alpha a_0^2$. The Zeeman energy is $b(L_{\hat{B}}+2S_{\hat{B}})$. The electron spin is free, so every spatial result below is duplicated with an added $\pm b$.

For a magnetic field parallel to $z$, the old magnetic quantum number $m$ remains good and the first-order energy levels areThe two $s$ orbitals have zero orbital angular momentum, so only their electron spin contributes at this order.

For a magnetic field parallel to $x$, the expectation of $L_x$ in each individual $p_m$ orbital vanishes. One must still check the degenerate $m=\pm 1$ subspace: its projected $L_x$ is zero as well. Thus there is no first-order orbital splitting in a sufficiently weak transverse magnetic field. Spin still contributes $\pm b$.

The transverse orbital Zeeman mixing can be seen without assuming its size. Put $E_0=-\mathrm{Ry}/4+3\epsilon$, $E_t=-\mathrm{Ry}/4+21\epsilon$, and $\Delta =E_t-E_0=18\epsilon$. In the real $p_x,p_y,p_z$ orbital basis, $p_x$ is unaffected while $p_y,p_z$ have off-diagonal matrix elements of modulus $b$. Diagonalizing this two-dimensional Hamiltonian gives the spatial energy eigenvaluesWhen $b\ll \Delta$, their shifts relative to the earlier levels are $0,+b^2/\Delta ,-b^2/\Delta$, with $\pm b$ added for electron spin. The displayed square-root expression also handles $b$ comparable to $\Delta$, provided coupling to other principal shells stays negligible. The $2s$ orbital retains zero orbital correction.

These quadratic orbital estimates keep the enhanced contribution from mixing the split $2p$ levels. Minimal magnetic minimal coupling also produces $e^2{B}^2{r}_{\perp }^2/(8m_e)$; its expectation value is positive and must be added for a full order-$B^2$ calculation. For example it gives $e^2{B}^2{a}_0^2/(4m_e)$ for $1s$. It is parametrically smaller than the $2p$ mixing term when $\epsilon \ll \mathrm{Ry}$.