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The initial quantum state is a coherent state. Since $a|\alpha ⟩=\alpha |\alpha ⟩$ and the state is normalized, its mean occupation number is $N=⟨a^{†}a⟩=|\alpha {|}^2$. Each quantum harmonic oscillator energy eigenstate acquires the phase $e^{-i\omega (n+1/2)t}$, soThe prefactor is a global phase and does not change an expectation value. Inverting the definitions of the annihilation operator and creation operator gives $x=\sqrt{\hslash /(2m\omega )}(a+a^{†})$. If $\alpha =\sqrt{N}{e}^{i\phi }$, thenFor a classical harmonic oscillator with amplitude $A$, the conserved energy is $E=m{\omega }^2{A}^2/2$. Setting $E=\hslash \omega N$ gives exactly the same amplitude, $A=\sqrt{2\hslash N/(m\omega )}$. Thus these coherent-state oscillator expectation values follow the classical orbit.

The full quantum mean energy is nevertheless $⟨H⟩=\hslash \omega (N+1/2)$: the extra zero-point energy belongs to the nonzero position and momentum uncertainties required by the Heisenberg uncertainty relation, rather than to the motion of the packet centre. In particular, $N=0$ gives zero mean displacement but a finite ground-state width. A coherent state follows a classical mean trajectory while retaining finite position and momentum uncertainties.

In the normalized plane wave basis, the only nonzero potential matrix elements areThus a useful small parameter is $|\lambda |/E_L\ll 1$, which suppresses admixture of well-separated energy levels. First-order nondegenerate perturbation theory further requires $|\lambda |/2\ll |E_n-E_{n\pm 1}|$ for the coupled states. This latter condition fails near a half-integer $\alpha$ even for very small $\lambda$; there one must use degenerate perturbation theory in the nearly degenerate pair. Smallness is measured against the gaps to the other states, not the vanishing gap inside this pair.

Near $\alpha =1/2$, keep $n=0,1$. The resulting Hamiltonian operator matrix and its eigenvalues areIn particular,For positive $\lambda$, the lower quantum state at the crossing is the symmetric combination of $n=0,1$, and the upper state is the antisymmetric combination. A negative $\lambda$ exchanges these combinations but leaves the ordered energy eigenvalues unchanged.

This cosine-potential gap in a quantum ring appears in the middle panel above: each lowest-branch crossing opens into an avoided crossing of gap $|\lambda |$ to first order. Away from these crossings, the diagonal matrix elements vanish, so the leading shifts are second order. At integer $\alpha$, the two first-excited plane waves differ by two units of $n$ and therefore have no first-order coupling; their smaller splitting begins at second order. The numerical plot includes that splitting.

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.

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.

The Pauli matrix ${\sigma }_x$ flips the spin with unit matrix element. A nonzero oscillator matrix element changes exactly one occupation number, through a creation operator or an annihilation operator:For a spin flip, the spin energy change divided by $\hslash$ is $-s_{\sigma }\Omega$. Thus creation and annihilation in mode $j$ have total frequency changes ${\omega }_j-s_{\sigma }\Omega$ and $-{\omega }_j-s_{\sigma }\Omega$, respectively. Distinct modes or different occupation changes lead to orthogonal final quantum states, so their probabilities add. Fermi's golden rule consequently givesThe Dirac delta function is even, accounting for the sign in the annihilation term. Since all ${\omega }_j,\Omega >0$, an initially up spin can only emit an oscillator quantum, while an initially down spin can only absorb one. Writing the oscillator density of states per unit angular frequency as $g(\omega )={\sum }_j\delta (\omega -{\omega }_j)$, the continuum limit givesThe $+1$ permits emission even from the oscillator vacuum; absorption requires a quantum already present. The notation $n_{\Omega }$ assumes a common or smoothly specified occupation at the resonant frequency. If several resonant modes have different occupations, it denotes their density of states weighted mean, so that $g(\Omega )n_{\Omega }={\sum }_j{n}_j\delta (\Omega -{\omega }_j)$ after continuum smoothing. This is the golden-rule relaxation of a spin coupled to an oscillator bath.

The canonical anticommutation relations make $(a^{†}{b}^{†}{)}^2=0$, so the proposed exponential function terminates exactly:Use the inverse Bogoliubov transformation $c=ua-v{b}^{†}$, $d=v{a}^{†}+ub$, and the actions $a|11⟩=b^{†}|0⟩$ and $b|11⟩=-a^{†}|0⟩$. The two vacuum state conditions becomeBoth therefore require $B=v/u$. Normalizing this quantum state gives $1=A^2(1+B^2)$. Choosing positive $A$, which fixes an irrelevant overall global phase, yields $A=u$ because $u^2+v^2=1$. Thus the two-mode fermionic paired vacuum isThe other sign for $A$ describes the same physical quantum state. The positive relative coefficient is fixed by the paper's pairing order and the convention $|11⟩=a^{†}{b}^{†}|0⟩$.

As a direct eigenvector check, $\Delta v=(E-\epsilon )u$ and $\Delta u=(E+\epsilon )v$ implyIt is therefore the unique ground state, as also follows from positive quasiparticle excitation energy $E$. It has definite even fermion parity but is not an eigenstate of the original total number operator: the empty-pair and occupied-pair probabilities are $u^2$ and $v^2$. In particular $⟨N_a⟩=⟨N_b⟩=v^2$. The pair amplitude is $⟨ab⟩=-uv$, consistently with $ab|11⟩=-|0⟩$.

For the limiting check $\Delta \to 0^{+}$ at fixed positive $\epsilon$, $A\to 1$, $B\to 0$, so $|\tilde{0}⟩\to |0⟩$. For $\epsilon \to 0^{+}$ at fixed positive $\Delta$, $A\to 1/\sqrt{2}$, $B\to 1$, giving equal amplitudes for the empty and occupied pair. These checks also fix which branch of the Bogoliubov transformation produces the ground state.

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.

Differentiating the specified rotating-frame amplitudes gives the time-independent Schrödinger equationThe characteristic polynomial is ${\lambda }^2-({\delta }^2+{\Omega }^2)/4=0$, henceFor $\Omega \ne 0$, corresponding normalized eigenvectors are proportional to $(\Omega ,2{\lambda }_{\pm }-\delta {)}^T$. Their arbitrary complex coefficients evolve as $e^{-i{\lambda }_{\pm }t}$; this solves the amplitude equations for any initial quantum state.

Restoring the common energy origin $\overline{E}=(E_1+\hslash \omega +E_2)/2$, the two dressed state energy eigenvalues areThus their positive energy separation increases byEquivalently, the branches connected to $E_1^{\prime }=E_1+\hslash \omega$ and $E_2$ shift by $+\hslash {\Omega }^2/(4\delta )$ and $-\hslash {\Omega }^2/(4\delta )$ respectively. Their signed difference $E_1^{\prime }-E_2$ changes by $\hslash {\Omega }^2/(2\delta )$, which is the printed expression with a signed convention. For negative Rabi detuning, an actual positive separation still increases; for example at $\delta =-10\Omega$ it cannot have the negative change implied by reading the printed expression as an unsigned gap. These opposite AC Stark shifts describe level repulsion.

The finite nuclear size correction perturbation is unchanged for the same lead atomic nucleus. Its leading effect on one occupied $1s$ orbital is still proportional to that orbital's contact density,Other electrons screen the nuclear attraction and alter the self-consistent $1s$ wavefunction, usually reducing its contact density and hence its positive shift relative to the bare hydrogen-like ion. The reduction is modest for a deep $1s$ orbital: it penetrates well inside most other shells and still samples nearly the full $Z=82$ attraction. Replacing $Z$ by the neutral atom's asymptotic charge one would be inappropriate for this core orbital.

A neutral lead atom has two $1s$ electrons. Their contributions add in a frozen-orbital estimate of total atomic energy, roughly twice the per-electron shift, with relaxation and correlation corrections. An experimentally observed transition frequency again depends on the difference between the finite-size shifts of both participating many-electron quantum states. A quantitative neutral-lead result requires a screened relativistic many-electron calculation, not the one-electron formula with a single universally valid effective charge.

Rabi oscillations require a coherent drive with a stable phase over several population cycles and an isolated, appreciably coupled pair of quantum states. For large-amplitude oscillations, the Rabi detuning must be comparable to or smaller than the Rabi angular frequency. The population lifetime, optical coherence time, transit time and drive coherence time should all exceed $2\pi /{\Omega }_R$ by enough to resolve the cycles. An ensemble also needs sufficiently uniform Rabi frequencies and Rabi detunings that phase averaging does not wash the oscillations out. The usual sinusoidal formula additionally assumes the rotating-wave approximation.

The Einstein coefficients describe incoherent transition rates, rather than the evolving optical probability amplitudes. Their simplest use is appropriate for broadband, randomly phased radiation, with field correlation time short relative to population evolution, or for rapidly dephased chemical atoms whose optical coherences can be eliminated. The radiation energy density per unit frequency must be smooth over the relevant spectral line. Stimulated upward and downward transitions and spontaneous emission then enter rate equations, without predicting coherent population return. A short observation time can give a small excitation probability even for a coherent field; that condition alone does not justify an Einstein coefficients rate description. Coherent laser irradiation can also admit steady rate equations after optical coherence has relaxed, with the appropriate saturation response.

Fix the qubit polarization convention by $\rho =(I+\vec{P}\cdot \vec{\sigma })/2$, where the Pauli matrices are ordered in the basis $(|1⟩,|2⟩)$ and ${\sigma }_z=|1⟩⟨1|-|2⟩⟨2|$. Thus the ground state is the north pole of the Bloch sphere. In a rotating frame and within the rotating-wave approximation, choose the drive phase and detuning sign so thatFor example, with this ground-state convention one may take $\Delta ={\omega }_L-{\omega }_0$ and choose the transverse coupling positive. The Bloch vector precesses around the effective field $(\Omega ,0,\Delta )$ at angular frequency ${\Omega }_R=\sqrt{{\Omega }^2+{\Delta }^2}$, tracing a circle at fixed projection on that axis. Its length is conserved under coherent unitary time evolution. On resonance the axis is transverse and the Rabi oscillation can fully invert an initially ground-state atom. Away from resonance the axis tilts, andThere is no relaxation towards an equilibrium Bloch vector in this ideal model. An inhomogeneous ensemble can nevertheless lose its averaged qubit polarization through dephasing even without spontaneous emission; the circle description assumes a common drive and detuning.

For $|a{|}^2+|b{|}^2=1$, the stated quantum state givesThe diagonal elements are the two state populations. The off-diagonal elements are quantum coherences: they retain the relative quantum phase and determine interference under a subsequent pulse. This is a pure state, even if both populations are nonzero: ${\rho }^2=\rho$, $\mathrm{Tr}{\rho }^2=1$, and $|\vec{P}|=1$. A mixed state averages projectors over preparation probabilities and generally has $\mathrm{Tr}{\rho }^2<1$. Equal populations alone do not distinguish an equal coherent superposition from an unpolarized mixture.

For use in all three cases, multiplication of the gates gives the Hadamard-phase-Hadamard qubit rotationThe global phase cancels in ${\rho }^{\prime }=U\rho U^{†}$. Thus the Bloch vector map is

The final unlabelled Ramsey spectroscopy comparison applies to the three cases as follows. In an atomic clock, an initial coherent pulse prepares a superposition, a free interval $T$ accumulates a relative quantum phase proportional to detuning times $T$, and a final coherent pulse converts that phase to a population. Here $\alpha$ plays the role of that accumulated phase, with sign and fringe offset set by pulse conventions. In (a), the first Hadamard gate creates the needed superposition and the final gate reveals full-contrast Ramsey interferometry. In (b), the first Hadamard gate instead puts the state in $|1⟩$, so the intervening phase gate has no relative quantum phase to imprint: the output is independent of $\alpha$. In (c), the unpolarized density matrix remains unchanged under every gate, so the ensemble has no Ramsey interferometry contrast. A coherent unitary gate alone cannot initialize a maximally mixed ensemble into a pure clock state.

The Ramsey interferometry analogy concerns preparation, phase accumulation, and readout; a Hadamard gate is not literally a transverse $\pi /2$ rotation on every input. In this basis $H=R_y(\pi /2){\sigma }_z$, and its Bloch sphere action is a $\pi$ rotation about $(\hat{x}+\hat{z})/\sqrt{2}$, up to a global phase. The phase conventions of physical Ramsey spectroscopy pulses must be specified to compare their outputs for arbitrary initial states.

The squared angular momentum and one chosen component can have simultaneously sharp values. All three components cannot have simultaneously sharp values in a nonzero-$j$ state. The possible measured component values are $m\hslash$, while the squared magnitude is $j(j+1){\hslash }^2$. This concerns the quantum state, rather than imperfect experimental resolution. The Robertson uncertainty relation, for example,quantifies the restriction; its right-hand side may vanish in some states, without making all three components simultaneously sharp.

Separation of variables makes the angular factor a spherical harmonic. Applying the Quantum Hamiltonian givesConsequently $R{Y}_{lm}$ is an energy eigenfunction provided the radial factor satisfiesThis is the radial Schrödinger equation for a central potential, here with the attractive Coulomb potential. An arbitrary $R$ does not give an eigenfunction; regularity, decay and wavefunction normalization select admissible bound quantum states.

Multiply the first-order equation by ${\Psi }_i^{(0)\ast }$ and integrate. The first term vanishes because Hermitian conjugation moves the unperturbed Hamiltonian onto the known bra:Here $E_i^{(0)}$ is real. The remaining equation isUsing wavefunction normalization therefore yieldsThus the first-order energy coefficient is the perturbation's expectation value in the unperturbed quantum state.

Inside the infinite square well, the stationary wavefunctions can be chosen real:They vanish outside the well and at its impenetrable endpoints. A sine meets the left boundary condition; the right one requires $\sin (n\pi )=0$. The putative $n=0$ function is identically zero, so it is not a quantum state. The constants $C_n$ are fixed by wavefunction normalization.

If two fermions occupied the same complete spin orbital $u$, their antisymmetrized product would beThe zero vector cannot represent a normalized quantum state. This is the Pauli exclusion principle: at most one identical fermion occupies any complete one-particle state. Two electrons may occupy the same spatial orbital with opposite spins, because $a\alpha$ and $a\beta$ are different spin orbitals.

Quantum tunnelling is penetration of, or transmission through, a finite potential barrier into a classically forbidden region, where the total energy is less than the potential energy. The wavefunction generally remains nonzero there, so the Born rule assigns a nonzero probability of detection. This does not require an increase in total energy; it is the classical relation between a definite position and a definite kinetic energy that cannot be imposed on the quantum state. For a bound quantum harmonic oscillator, the relevant quantity is the probability of finding the particle beyond its classical turning points; it is not an escaping transmitted beam.

Fix the positive lobes of the real atomic orbitals along the printed positive axes, and write ${\varphi }_1=p_x(1)$, ${\varphi }_4=p_x(4)$, ${\varphi }_5=p_y(5)$ and ${\varphi }_8=p_y(8)$. A coordinate model consistent with the figure is $r_1=(0,a,-b)$, $r_4=(0,-a,-b)$, $r_5=(a,0,b)$ and $r_8=(-a,0,b)$, with $a,b>0$. For the D2d molecular point group, take the two transverse twofold axes along $x+y$ and $x-y$, with vertical mirrors $xz$ and $yz$. The $A_2$ character table row on $(E,2S_4,C_2,2C_2^{\prime },2{\sigma }_d)$ is $(1,1,1,-1,-1)$. The character projection operator isThe eight signed images needed for this projection areso $P_{A_2}{\varphi }_1=({\varphi }_1-{\varphi }_4-{\varphi }_5+{\varphi }_8)/4$. Under the standard orthonormal atomic orbital approximation its squared norm is $4/16=1/4$. Therefore the normalized symmetry-adapted linear combination isAn overall minus sign describes the same quantum state; changing one local atomic orbital phase requires changing its coefficient too. If intersite orbital overlap were retained, normalization would instead use the overlap matrix.