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For a nondegenerate parity-symmetric ground state in an external electric field, write the perturbation as $V=-E\hat{d}$. The first-order state correction givesThe positive coefficient $\alpha$ is the electric polarizability along the applied direction. Meanwhile second-order nondegenerate perturbation theory gives $\delta E_0^{(2)}=-\alpha E^2/2$. Thus the induced electric dipole moment satisfies $d=-2\delta E_0^{(2)}/E$, not $-\delta E_0^{(2)}/E$. The Hellmann–Feynman theorem independently gives $d=-\partial E_0/\partial E$.

For a real scalar lattice-periodic potential, let $|n⟩$ be a nondegenerate zone-centre periodic eigenstate with energy $E_n$. Conjugation by $e^{i\mathbf{k}\cdot \mathbf{r}}$ gives $H(\mathbf{k})=H(0)+\hslash \mathbf{k}\cdot \mathbf{p}/m+{\hslash }^2{k}^2/(2m)$. The zone-centre state can be chosen real, so $⟨n|\mathbf{p}|n⟩=0$. Second-order nondegenerate perturbation theory then givesTime-reversal symmetry makes this isolated spinless band even in $\mathbf{k}$. In a direction $\mathbf{e}$, the curvature givesA degeneracy requires a matrix treatment before extracting curvatures; a nonlocal potential or spin-orbit terms can also alter the simple momentum vertex.

Perturbation theory for an isolated eigenvalue with a one-dimensional eigenspace. First-order nondegenerate perturbation theory gives the diagonal perturbation expectation, while second-order nondegenerate perturbation theory accounts for coupling to other unperturbed eigenstates through energy denominators. Symmetry can permit its use within one block even if another, uncoupled symmetry block has the same unperturbed eigenvalue.

For a bound energy eigenstate with a nondegenerate energy eigenvalue of an even one-dimensional potential, the wavefunction can be chosen with definite parity. A uniform electric field $\mathcal{E}$ gives the electric-dipole interaction $H^{\prime }=-q\mathcal{E}x$, which is odd under reflection. Hencesince $x|{\psi }_n(x){|}^2$ is odd. Second-order nondegenerate perturbation theory then gives the leading allowed Stark effect shift:Only opposite-parity intermediate states have nonzero position matrix elements. More generally, reflection maps $H(\mathcal{E})$ to $H(-\mathcal{E})$, so an analytic nondegenerate energy level is an even function of the field. This explains the absence of all odd orders and the usual quadratic Stark effect.

A level separation changes by the difference of the two quadratic coefficients. Symmetry alone does not guarantee a nonzero differential shift: in a displaced quantum harmonic oscillator every level moves by the same $-q^2{\mathcal{E}}^2/(2m{\omega }^2)$, leaving every spacing unchanged. Degenerate states would instead require degenerate perturbation theory and can split linearly; the nondegeneracy of one-dimensional bound states applies to ordinary isolated well levels.

The unperturbed infinite square well is invariant under the parity operator. Its one-dimensional energy eigenvalues are nondegenerate, so each energy eigenstate has definite parity. Its position expectation value therefore vanishes: $|{\varphi }_n(x){|}^2$ is even, while $x$ is odd. The first-order nondegenerate perturbation theory correction is consequentlyThe electric field does mix opposite-parity quantum states, and second-order nondegenerate perturbation theory contains two factors of $eEx$. Its leading contribution is thus proportional to $E^2$: this is a quadratic Stark effect. More generally, applying the parity operator changes $H(E)$ into $H(-E)$, so their corresponding energy eigenvalues agree. An analytic expansion about zero electric field contains only even powers of $E$. We assume $e|E|a$ is small compared with the unperturbed excitation scale.

Use zero-based labels to agree with ${\varphi }_0$ in the later parts. The normalized infinite square well energy eigenstates and energy eigenvalues areThe position matrix elements in a symmetric infinite square well, obtained by integrating the product of the two wavefunctions against $x$, areThe integral in the question uses positive integer labels; replacing them by $k+1,n+1$ is essential here. Only opposite-parity states, $k+n$ odd, contribute, as also follows from the parity operator selection rule.

Second-order nondegenerate perturbation theory now gives the requested infinite sum:In fully explicit form this isThe symbol $m$ here denotes the electron mass, not a summation index. For the ground state $n=0$, every denominator in the first form is negative, so the ground energy level moves downward. For excited states, contributions from lower and higher energy levels have opposite signs.

The electron's electric dipole moment is $\mathbf{d}=-e⟨x⟩\hat{\mathbf{x}}$. It vanishes in the unperturbed ground energy eigenstate. The first correction to the wavefunction is linear in the electric field and has the opposite parity; its interference with the unperturbed state therefore gives a nonzero position expectation value of first order.

In detail, the normalized ground quantum state, to the order needed, isThe normalization correction starts at second order and does not affect the linear term below. The two cross terms giveThe absence of an $E^2$ term follows from the parity operator: $⟨x⟩$ changes sign under field reversal. Comparing with the second-order nondegenerate perturbation theory energy sum yieldsThus the induced electric dipole moment points along the electric field, with positive electric polarizability. The induced dipole moment and quadratic energy shift obey $\delta {ϵ}_0^{(2)}=-{\alpha }_{\mathrm{pol}}{E}^2/2$. This factor of one half accounts for the energy needed to induce the dipole. As a check, the Hellmann–Feynman theorem gives $d_x=-\partial {ϵ}_0/\partial E$, with the same result.

Normalize the trial quantum state as $(|{\varphi }_0⟩+c|{\varphi }_1⟩)/\sqrt{1+c^2}$. With the phases used above, the off-diagonal position matrix element is $x_{01}=-32a/(9{\pi }^2)$. DefineThe diagonal perturbation matrix elements vanish by parity, so the Rayleigh quotient isThe stationarity equation is $W+\Delta c-W{c}^2=0$. The minimum continuously connected to the unperturbed ground energy eigenstate hasEquivalently, diagonalize the Hamiltonian operator matrix in this two-dimensional trial space. Its lower eigenvalue isThereforeThis retains exactly the $k=1$ term of the full ground-state second-order nondegenerate perturbation theory sum. Every omitted term is negative, so the full quadratic correction is more negative than this restricted one. This is consistent with the Rayleigh-Ritz variational principle: minimizing over a two-state subspace gives an upper bound on the exact ground energy. The bound applies to the unexpanded two-state minimum; a truncated series is to be compared order by order.

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.

Write $|\uparrow ⟩,|\downarrow ⟩$ for the two $S_3$ eigenstates, of eigenvalues $\pm \hslash /2$. The spin-spin interaction can be evaluated usingFor $|\beta |\gg |\alpha |$, take $H_0=\beta (S_3^{(1)}-S_3^{(2)})/\hslash$ and $V=\alpha {\mathbf{S}}^{(1)}\cdot {\mathbf{S}}^{(2)}/{\hslash }^2$. The unperturbed energy eigenvalues are $\beta ,-\beta ,0,0$ on $|\uparrow \downarrow ⟩,|\downarrow \uparrow ⟩,|\uparrow \uparrow ⟩,|\downarrow \downarrow ⟩$, respectively. For an isolated normalized energy eigenstate $|n⟩$, first-order nondegenerate perturbation theory gives $\Delta E_n^{(1)}=⟨n|V|n⟩$. The two antiparallel spins have expectation $-\alpha /4$, soFor the zero-energy degenerate eigenspace, degenerate perturbation theory requires diagonalizing the restriction of $V$. On the ordered basis $(|\uparrow \uparrow ⟩,|\downarrow \downarrow ⟩)$ it is $(\alpha /4)I$: the ladder operators cannot take one parallel state to the other. Indeed neither parallel state couples to anything else under $H$, so the remaining two levels are exactly $\alpha /4$, retaining their twofold quantum degeneracy.

For $|\alpha |\gg |\beta |$, take $H_0=\alpha {\mathbf{S}}^{(1)}\cdot {\mathbf{S}}^{(2)}/{\hslash }^2$ and $V=\beta D$, where $D=(S_3^{(1)}-S_3^{(2)})/\hslash$. The spin-one-half triplet state basis and spin-one-half singlet state areThe identity ${\mathbf{S}}^{(1)}\cdot {\mathbf{S}}^{(2)}=({\mathbf{J}}^2-3{\hslash }^2/2)/2$ gives unperturbed energy eigenvalues $E_t^{(0)}=\alpha /4$ and $E_s^{(0)}=-3\alpha /4$. Direct action givesConsequently the restriction of $V$ to the entire triplet degenerate eigenspace is zero, so no first-order splitting is missed. The singlet expectation is also zero. In second-order nondegenerate perturbation theory, $\Delta E_n^{(2)}={\sum }_{r\ne n}|⟨r|V|n⟩{|}^2/(E_n^{(0)}-E_r^{(0)})$. Within the triplet, the corresponding second-order effective matrix is ${\beta }^2|t_0⟩⟨t_0|/\alpha$, already diagonal in this basis. Thus, through second order,The last two expressions have higher corrections beginning at $O({\beta }^4/|\alpha {|}^3)$, as the exact calculation in part (d) also verifies. For positive $\alpha$, coupling to the lower singlet raises the triplet's $M=0$ level and lowers the singlet; the signs are precisely the energy denominators above.

Let $H|n⟩=E_n|n⟩$, with nondegenerate eigenvalues, and expand the perturbed state as $|n⟩+\lambda |n^{(1)}⟩+\cdots$, choosing $⟨n|n^{(1)}⟩=0$. The first-order eigenvalue equation gives $E_n^{(1)}=V_{nn}$ and, after projection onto $m\ne n$, $⟨m|n^{(1)}⟩=V_{mn}/(E_n-E_m)$. Projecting the second-order equation onto $n$ then gives the second-order nondegenerate perturbation theory resultFor angular momentum, $j=0,1/2,1,\dots$, $m=-j,-j+1,\dots ,j$, and $J^2|jm⟩=j(j+1)|jm⟩$, $J_3|jm⟩=m|jm⟩$ in units $\hslash =1$.

Take $H_0=-\gamma B_3{J}_3$ with $\gamma B_3\ne 0$ and perturbation $-\gamma B_1{J}_1$. The diagonal matrix element of $J_1=(J_{+}+J_{-})/2$ vanishes. Only $m\pm 1$ contribute at second order. Their squared matrix elements are $[j(j+1)-m(m\pm 1)]/4$, and their unperturbed energy denominators are respectively $\gamma B_3$ and $-\gamma B_3$. ThusHence $\boxed{E_m=-\gamma B_{3}m-\gamma m{B}_1^2/(2B_3)+O(B_1^4)}$. Rotating the quantization axis to the field gives exact energies $-\gamma m_B\sqrt{B_3^2+B_1^2}$. Labeling each branch continuously from its original $m$ gives $E_m=-\gamma m{B}_3\sqrt{1+B_1^2/B_3^2}$, whose expansion agrees, including negative $B_3$. If $B_3=0$, the nondegenerate starting point fails and this expansion cannot be used.

Put $C=[A,B]$, which commutes with both operators by hypothesis. Differentiating $e^{\lambda A}B{e}^{-\lambda A}$ gives $C$, so this conjugate is $B+\lambda C$. Similarly the product $P=e^{\lambda A}{e}^{\lambda B}$ conjugates $A+B$ to itself: the two central commutator shifts cancel. HenceWith $F(0)=I$, the operator differential equation gives $F(\lambda )=e^{{\lambda }^{2}C/2}$. At $\lambda =1$ this proves the central-commutator Baker--Campbell--Hausdorff formulaThese formal manipulations apply on a suitable common domain, or to the oscillator exponentials below where the corresponding unitary identities are well defined.

The oscillator has $[a,a^{†}]=1$ and $H=\hslash \omega (a^{†}a+1/2)$. Its normalized states and energies areSince $\hat{x}=\sqrt{\hslash /(2m\omega )}(a+a^{†})$, put $\gamma =\mu \sqrt{\hslash /(2m\omega )}$. Taking $A=\pm i\gamma a^{†}$, $B=\pm i\gamma a$ gives $[A,B]={\gamma }^2$. The formula implies $e^{\pm i\mu \hat{x}}=e^{-{\gamma }^2/2}{e}^{\pm i\gamma a^{†}}{e}^{\pm i\gamma a}$. Averaging the two signs proves the requested normal ordering of the cosine.

Because $a|0⟩=0$, expansion of the remaining creation exponential givesOdd matrix elements vanish, the ground expectation is $e^{-{\gamma }^2/2}$, and the magnitude squared for $n=2p$ is $e^{-{\gamma }^2}{\gamma }^{4p}/(2p)!$. The nondegenerate second-order nondegenerate perturbation theory formula is $\Delta E_0=ϵV_{00}+{ϵ}^2{\sum }_{n>0}|V_{n0}{|}^2/(E_0-E_n)+O({ϵ}^3)$. ThereforeThe negative second-order sign comes from the higher unperturbed energies in every denominator.

For a normalized eigenstate $|n⟩$ with a nondegenerate energy eigenvalue, first-order nondegenerate perturbation theory and second-order nondegenerate perturbation theory give

Choose the $z$-axis along $\mathbf{E}$, so the perturbation isup to an irrelevant sign convention for the electron charge. By second-order nondegenerate perturbation theory,Parts (a) and (b) restrict the contributing bound states toFor hydrogen,and henceThereforeEvery denominator is negative, so the discrete-state contribution lowers the ground-state energy.

mass as band curvature. In a periodic potential, a weakly forced electron is usefully described by a wave packet confined to one energy band. Its group velocity isDifferentiating the velocity givesThis effective-mass tensor describes the band response, not a change of the electron's bare rest mass. Along a principal direction, a steep upward curvature gives a small positive mass and a flatter curvature a larger one. Near a band maximum the electron curvature and effective mass are negative; the corresponding missing-electron description uses positive electron hole masses. Anisotropy produces distinct principal masses, and strong nonparabolicity makes them momentum dependent. The single-band semiclassical description assumes fields weak and slowly varying enough to avoid substantial interband transitions.

Lattice symmetry and Bloch's theorem. Use the active spatial translation operator $T_{\mathbf{a}}\psi (\mathbf{r})=\psi (\mathbf{r}-\mathbf{a})$. A lattice-periodic scalar potential satisfies $V(\mathbf{r}+\mathbf{a})=V(\mathbf{r})$, while the kinetic term is translation invariant. Therefore $[H,T_{\mathbf{a}}]=0$. The lattice translations also commute with one another, so they can be diagonalized simultaneously with $H$, including within a degenerate energy subspace.

For a common eigenstate, write $T_{\mathbf{a}}\psi =t(\mathbf{a})\psi$. Unitarity gives $|t(\mathbf{a})|=1$, and the group law gives $t(\mathbf{a}+\mathbf{b})=t(\mathbf{a})t(\mathbf{b})$. On primitive Bravais vectors ${\mathbf{a}}_j$, choose $t({\mathbf{a}}_j)=e^{-i\mathbf{k}\cdot {\mathbf{a}}_j}$. Every lattice vector is an integer combination of these generators, henceThe vector $\mathbf{k}$ is defined modulo a reciprocal lattice vector. The band index labels the different energy eigenstates with the same translation character. Define $u_{n\mathbf{k}}(\mathbf{r})=e^{-i\mathbf{k}\cdot \mathbf{r}}{\psi }_{n\mathbf{k}}(\mathbf{r})$. The phase factors cancel under a lattice translation, proving Bloch's theorem in its usual form:This is the Translation-character proof of Bloch theorem; the commutator guarantees a basis of such states, even when an arbitrary superposition of different translation characters is not itself a translation eigenstate.

Periodic Hamiltonian. Acting once with momentum gives $\mathbf{p}(e^{i\mathbf{k}\cdot \mathbf{r}}u)=e^{i\mathbf{k}\cdot \mathbf{r}}(\mathbf{p}+\hslash \mathbf{k})u$. Applying it again and cancelling the common plane-wave factor yieldsThe Bloch Hamiltonian acts on lattice-periodic functions in a unit cell. Expanding its square separates a zero-momentum Hamiltonian, a term linear in $\mathbf{k}$ and an identity term quadratic in $\mathbf{k}$.

Expansion about the zone centre. Let $|n⟩=u_{n0}$, $E_n={\epsilon }_n(0)$, and normalize all these states using a unit-cell inner product. For the real scalar Hamiltonian in the question, a nondegenerate zone-centre eigenfunction can be chosen real. Thenbecause opposite unit-cell faces cancel. Equivalently, time-reversal symmetry forbids a nonzero electric current in this nondegenerate spinless state. This explains why no linear energy term appears; it should not simply be omitted without a symmetry or extremum argument.

The first-order energy shift is therefore ${\hslash }^2{k}^2/(2m)$. In the second-order sum the quadratic term is proportional to the identity and has no off-diagonal matrix elements. Only the linear momentum vertex contributes. Second-order nondegenerate perturbation theory gives the momentum matrix-element expansion of band energyHermitian operator makes the two reciprocal matrix elements complex conjugates. All other periodic eigenstates at $\mathbf{k}=0$ enter the sum. The remainder is even because time-reversal symmetry gives ${\epsilon }_n(\mathbf{k})={\epsilon }_n(-\mathbf{k})$ near this isolated state. At a degeneracy the denominators signal the need for degenerate perturbation theory instead.

mass ratio and the printed formula. Write $p_{nl}^i=⟨n|p_i|l⟩$. Differentiating the quadratic energy yieldsFor a specified unit direction $\mathbf{e}$, the resulting scalar mass ratio isIn an isotropic three-dimensional band, averaging equivalent directions givesCoupling to lower bands contributes positively to inverse mass; coupling to higher bands contributes negatively. Their signs and matrix elements determine the actual curvature.

The original PDF prints $m^{\ast }={\hslash }^2[{\nabla }_{\mathbf{k}}^2{\epsilon }_n{]}^{-1}$. Taken literally as a three-dimensional Laplacian, this misses a factor of three for an isotropic scalar mass. The correct identities areThe printed expression would return $m/3$ even for the free dispersion ${\hslash }^2{k}^2/(2m)$. It is correct in one dimension, or if its second derivative is interpreted directionally. For completeness, its literal three-dimensional trace ratio would instead be $3+(2/m){\sum }_{l\ne n}|⟨n|\mathbf{p}|l⟩{|}^2/(E_n-E_l)$; that is the trace of the dimensionless inverse-mass tensor, not the usual scalar $m/m^{\ast }$.

The quadratic Stark effect is an energy level shift whose leading term is quadratic in an applied electric field. For a nondegenerate energy eigenstate of definite parity, the diagonal matrix element of an odd electric-dipole perturbation vanishes. Second-order nondegenerate perturbation theory givesEvery term is negative for the ground state. If field reversal is implemented by the parity operator, an analytic nondegenerate energy branch is even in the field. This symmetry explains the absence of odd powers; it does not apply without qualification to a degeneracy split linearly by the field.

The even, spherically symmetric hydrogen atom ground state has no permanent electric dipole, so a uniform electric field gives no first-order energy shift. The electric-dipole selection rules for hydrogen allow odd-parity excited states to mix in at second order, yielding a negative shift quadratic in the field.

Here there is a nondegenerate energy eigenvalue, so second-order nondegenerate perturbation theory applies. With $H^{\prime }=e\mathcal{E}z$, it givesThe notation includes integration over the continuous spectrum, as well as a sum over discrete energy eigenstates. All denominators are negative because $1s$ is the ground state. The positive electric polarizability ${\alpha }_{1s}$ therefore lowers its energy.^[ref]

An independent way to see the coefficient avoids truncating that sum. Define $E_{\mathrm{h}}=e^2/(4\pi {ϵ}_0{a}_0)$ and $f=e{a}_0\mathcal{E}/E_{\mathrm{h}}$. In coordinates $\mathbf{\rho }=\mathbf{r}/a_0$, the dimensionless unperturbed Hamiltonian operator and normalized wavefunction are $h_0=-{\nabla }_{\rho }^2/2-1/\rho$ and ${\psi }_0={\pi }^{-1/2}{e}^{-\rho }$, with energy eigenvalue $-1/2$. Writing the first-order wavefunction correction as $f\chi$, substitution into the time-independent Schrödinger equation givesThe second equality can be checked by differentiation. Its parity makes $\chi$ orthogonal to ${\psi }_0$. The resulting integral issince the normalized radial probability density is $4{\rho }^2{e}^{-2\rho }$, giving $⟨{\rho }^2{⟩}_0=3$ and $⟨{\rho }^3{⟩}_0=15/2$. Converting back to SI units gives the stated electric polarizability. The induced electric dipole moment is $-\partial \Delta E/\partial \mathcal{E}={\alpha }_{1s}\mathcal{E}$ and tends to zero with the electric field, unlike the selected degenerate branches' leading dipoles. Both calculations describe weak-field level shifts; a spatially uniform static electric field also allows eventual quantum tunnelling and ionization, which these real energy corrections do not calculate.

A hopping process through an intermediate configuration of different unperturbed energy, contributing to a low-energy effective description through perturbation theory. If an intermediate state costs $\Delta >0$, second-order nondegenerate perturbation theory gives a contribution $-|⟨a|T|0⟩{|}^2/\Delta$. Its amplitude is of order $t/\Delta$ and its energy correction of order $-t^2/\Delta$; a degenerate low-energy sector requires the corresponding degenerate perturbation theory before identifying the ground state.