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For an ideal projective measurement with the Lüders rule, condition on both an initial quantum state preparation and a final successful postselection. Its outcome probabilities are proportional to $|⟨b|P_j|a⟩{|}^2$, where $a$ is the forward-evolved initial state and $b$ the backward-evolved final state. The normalization must be nonzero. The expression is symmetric in these two boundary states, although its derivation uses the ordinary Born rule and conditional state update.

An atomic orbital is a one-electron spatial wavefunction used to describe an electron's state in a chemical atom. For a one-electron hydrogen atom, orbitals can be exact energy eigenstates; descriptions of many-electron atoms instead use an orbital approximation. A normalized atomic orbital has $\int |\varphi {|}^2{d}^3\mathbf{r}=1$, and the Born rule gives the position probability density $|\varphi {|}^2$. It is a function extending through space, not a prescribed classical orbit. ^[ref]

The linear combination of atomic orbitals combines these single-centre functions to approximate a molecular orbital. The orbital overlap measures their inner product, and their relative quantum phase controls the interference shown in molecular orbital theory.

Give Alice the first qubit $A$ and Bob the second $B$. Compare the Bell state $|{\Phi }^{+}⟩$ with a preparation that tosses a fair classical bit and gives both parties its value. Their density operators, written in the computational basis ordered $00,01,10,11$, areThey have identical diagonal quantum state populations. The off-diagonal entries of the Bell state retain quantum coherence between $00$ and $11$; the classical mixture has none in this basis.

If both parties perform a Pauli measurement of $Z$, the Born rule gives $P(00)=P(11)=1/2$ and $P(01)=P(10)=0$ for both preparations. Perfect agreement here therefore cannot establish entanglement: an ordinary shared random bit already explains it.

Now both measure $X$, whose normalized eigenstates are $|+⟩=(|0⟩+|1⟩)/\sqrt{2}$ and $|-⟩=(|0⟩-|1⟩)/\sqrt{2}$. Changing basis givesThe Bell state again has matching outcomes, each with probability $1/2$. For either product state $|00⟩$ or $|11⟩$, each of the four $X$ outcome pairs has probability $1/4$, so their classical mixture does too. Equivalently, the Pauli correlator $⟨X\otimes X⟩$ is one for the Bell state and zero for this mixture, while $⟨Z\otimes Z⟩$ is one for both.

Taking a partial trace gives ${\rho }_A={\rho }_B=I_2/2$ for both preparations. Thus every measurement confined to Alice's system has the same statistics in the two cases, and so does every measurement confined to Bob's. They reveal the difference by comparing records through classical communication. Conditional on Alice's result, Bob can predict a matching $X$ result for the Bell state; without that result, his outcomes remain evenly split. An uncommunicated local quantum channel, including a measurement with its outcome discarded, leaves his reduced density matrix unchanged. This is quantum no-signalling, even when conditional states change. ^[ref]

The Von Neumann entropy makes the joint-versus-local distinction numerical. With base-two logarithms, the Bell state has eigenvalues $1,0,0,0$, giving $S(AB)=0$, whereas the mixture has $1/2,1/2,0,0$, giving $S(AB)=1$. Both have $S(A)=S(B)=1$. Their quantum mutual information $I(A:B)=S(A)+S(B)-S(AB)$ is consequently two and one bits, respectively. The value two is not two readable classical bits in either local qubit: the matching $Z$ records have ordinary mutual information one bit in both cases. Random records can come from a globally pure state. ^[ref]

These two matching-axis measurements distinguish the specified preparations; they alone are not a test of a Bell inequality. A local hidden-variable theory could assign shared random answers separately to these two axes. Bell theorem concerns incompatible correlations across a suitable larger collection of measurement settings. Bell's 1964 paper established the obstruction for local hidden-variable descriptions of the predicted correlations. ^[ref]

An isolated qubit that acquires only a global phase has unchanged measurement probabilities. To reveal the Berry phase, use two coherent paths of a Mach-Zehnder interferometer, represented by a path qubit. In one arm the internal spin one-half qubit follows the loop; in the reference arm it stays in its starting energy eigenstate. Assume equal arm amplitudes, identical final internal states, cancelled relative dynamical phases, and calibrated fixed apparatus phases. In the model above, hold the reference Hamiltonian operator at its initial value for the same duration. Both arms then have energy eigenvalue $-\Delta /2$ and acquire the same dynamical phase $\Delta T/(2\hslash )$, so their relative dynamical phase vanishes in the ideal limit of the adiabatic theorem.

The joint quantum state before recombination then factors asThe Berry phase is now a relative quantum phase between the two paths. The calibrated plus output projects onto $|+⟩=(|\mathrm{ref}⟩+|\mathrm{loop}⟩)/\sqrt{2}$. The Born rule givesFor the Berry phase of a Bloch-sphere latitude, the plus-port probabilities at $\theta =0,60^{\circ },90^{\circ },180^{\circ }$ are respectively $1,1/2,0,1$. This ideal Mach-Zehnder interferometer measurement cannot distinguish $\gamma$ from $-\gamma$ or $\gamma +2\pi$ by itself; scanning a known reference phase can resolve the sign. An uncancelled relative dynamical phase would shift the fringe as well.

The Born rule connects a quantum state to measurement probabilities. Let $\{|j⟩\}$ be a complete orthonormal basis, finite or countably infinite, for a Hilbert space, and letAn ideal measurement distinguishing these basis vectors returns label $j$ with probabilityThis assignment is a physical measurement rule. Its compatibility with total probability one follows from orthonormality and normalization:The probabilities are the squared moduli, not the amplitudes themselves or the squares $a_j^2$. ^[ref].

If the basis is an eigenbasis of an observable, the reported numerical value is its eigenvalue. Several vectors can share one eigenvalue; the probability of that value is then the sum over the corresponding basis labels. More generally, a projective measurement with orthogonal projections $P_r$ assignsfor a pure state and a general density matrix $\rho$, respectively. This also covers mixed states and degenerate eigenspaces. The Born rule determines outcome statistics; the ideal conditional state change is specified separately by the Lüders rule. See projective measurement for that formulation and its assumptions. ^[ref].

For a worked example, take the normalized qubit quantum stateThe squared moduli add to $3/4+1/4=1$. A computational-basis measurement, equivalently a measurement of the $Z$ Pauli matrix, hasThese probabilities do not depend on the relative quantum phase $\varphi$. Now choose the Hadamard basiswhose vectors are eigenstates of the $X$ Pauli matrix, also used by the Pauli X gate. The new probability amplitudes and probabilities areBoth probabilities are nonnegative and their sum is one. The relative quantum phase becomes visible because the two probability amplitudes add before their squared modulus is taken:

A Hadamard gate followed by a computational-basis measurement realizes these $X$ statistics, since $H|\pm ⟩=|0⟩,|1⟩$, respectively. Compare the two bases using fresh, identically prepared copies: a preceding measurement may change the state. The quantum superposition section shows why replacing the preparation by the mixed state $\mathrm{diag}(3/4,1/4)$ keeps the $Z$ statistics but gives $p_{+}=p_{-}=1/2$ for every $\varphi$.

The usefulness of the Born rule is this conversion from linear algebra to experimental predictions: calculate overlaps in the basis actually measured, then take squared moduli. Its appealing geometry is that changing basis redistributes probability while preserving total squared norm. The same rule relates an energy eigenstate expansion to an energy measurement and a position wavefunction to a probability density.

Born's 1926 paper on quantum scattering interpreted the outgoing-wave coefficients in terms of the probabilities of collision outcomes; a corrective footnote specified proportionality to the square of the amplitude. This is a historical scattering formulation, rather than the general density matrix formula above. ^[ref]; ^[ref].

The scattering interpretation connects an incoming preparation to the relative frequency of outgoing directions and final atomic states. Max Born's 1926 paper treats a distant incoming electron and a chemical atom, expands the outgoing wavefunction into final atomic states, and imposes conservation of energy. Its translated correction footnote specifies the square of the coefficient; the modern complex modulus notation below is ours.^[ref]

In his 11 December 1954 lecture, Max Born recalled the difficulty of interpreting bound electrons alone. He instead described an incident electron wave generating an outgoing spherical wave, with direction-dependent squared amplitude determining relative scattering probabilities. Distinct final atomic states describe excitation with corresponding electron energy loss. This is a retrospective account of an interpretation, rather than the report of a new apparatus.^[ref]

The distinction from the modern Born rule matters. The historical question was which collision outcome occurs: a direction of motion and a final atomic state. The general projective measurement formula applies to arbitrary observables, including degenerate outcomes and mixed states; a positive operator-valued measure describes still more general detector statistics. Those formulations should not be read back as the explicit contents of the short 1926 scattering paper. Nor does the scattering interpretation itself supply a rule for the conditional post-measurement state.

Actual experimental settings are described in the Davisson–Germer experiment and the Franck-Hertz experiment. The former scans collected electric current as an electron beam scatters from prepared nickel; changing direction, accelerating voltage and surface preparation probes electron diffraction. The latter uses acceleration through mercury vapor and a retarding collector to infer discrete energy losses from current minima, with vapor density and retarding settings as controls. Angular resolution and surface backgrounds limit the first inference; initial energy spread and collision positions limit the second. These linked experiments supply the preparation, apparatus and readout; the examples below are original calculations, not Born's measured data.

Choose the qubit computational basis $|0⟩,|1⟩$, also called the $Z$ basis, and the Hadamard basis $|\pm ⟩=(|0⟩\pm |1⟩)/\sqrt{2}$, also called the $X$ basis. Compare a coherent preparation of $|+⟩$ with choosing $|0⟩$ or $|1⟩$ at random with equal probabilities and discarding that label:These are original ideal preparation models. Their $Z$-basis probabilities are both $(1/2,1/2)$, because their quantum state populations agree. Their $X$-basis probabilities are respectively $(1,0)$ and $(1/2,1/2)$. Indeed $⟨+|{\rho }_{+}|+⟩=1$, whereas $⟨+|I/2|+⟩=1/2$. The missing off-diagonal quantum coherence therefore changes a prediction that the common populations cannot determine.

For a relative quantum phase $\varphi$, the coherent family instead hasThe last formula follows by adding or subtracting the two probability amplitudes before taking the squared modulus. At $\varphi =\pi$, the state is $|-⟩$ and the $X$ outcomes switch to $(0,1)$, while the $Z$ outcomes remain $(1/2,1/2)$. In contrast, $-|+⟩$ changes both components by the same global phase and retains the $X$ outcomes $(1,0)$. In photon polarization, the identification $|0⟩=|H⟩$, $|1⟩=|V⟩$ makes $|+⟩$ and $|-⟩$ the two orthogonal diagonal linear polarizations; these labels describe measurement bases, not spatial axes for photon spin.

Even perfect statistics in one basis cannot certify a preparation. The above $Z$ data fit both density matrices. Conversely, distinct preparation histories can yield the same quantum state:The off-diagonal terms cancel in the right-hand ensemble. Every measurement on the qubit alone then has identical probabilities for those two histories. A retained classical label would allow conditioning on different members of the quantum state ensemble; it is extra information beyond the unlabelled density operator.

A deterministic interpretation with a definite particle configuration guided by the wavefunction. The latter obeys the Time-dependent Schrödinger equation, while the particle follows the guidance equation. A Born rule distribution of initial positions is preserved by quantum equilibrium equivariance. The guidance law restricts admissible initial velocities, even when trajectories are rewritten as a second-order force equation.

The study of choices under uncertainty and consistency conditions on preferences. In a quantum application, recovering Born rule weights from preferences requires specifying how physically equivalent games and irrelevant branch refinements affect value; it is not a consequence of decoherence alone.

A finite-dimensional density operator $\rho$ represents a quantum state on a Hilbert space. It is Hermitian, positive semidefinite, and has trace one:The density matrix is its matrix in a chosen orthonormal basis. In dimension $N$ it has $N^2-1$ real parameters: a Hermitian matrix has $N^2$, and fixing its trace removes one; positivity restricts the allowed values.

A quantum state ensemble of normalized pure states $|{\psi }_i⟩$ with positive probabilities $p_i$ givesZero-weight terms can be omitted. Conversely, the spectral theorem gives such an ensemble for every density operator, using its orthonormal eigenvectors and nonnegative eigenvalues, with zero eigenvalues omitted. A pure state has $\rho =|\psi ⟩⟨\psi |$; a mixed state needs at least two nonzero eigenvalues. ^[ref]

For a projective measurement with orthogonal projections ${\Pi }_a$, the Born rule isThis is the average of the component pure state probabilities. Positivity makes each outcome probability nonnegative, and ${\sum }_a{\Pi }_a=I$ makes them sum to one. The same density operator therefore predicts every measurement on the system without requiring a unique preparation history. ^[ref]

For a closed system, Schrödinger picture evolution under a unitary operator iswhen ${\rho }_H={\rho }_S(0)$ denotes the time-independent Heisenberg picture state and $U(0)=I$. In the Schrödinger picture the density operator evolves; in the Heisenberg picture the observables evolve instead, with identical measurement predictions. This unitary operator preserves the eigenvalues and hence the purity of a density operator. ^[ref]

A historical source for the probabilistic formulation of quantum mechanics is von Neumann's 1927 paper Wahrscheinlichkeitstheoretischer Aufbau der Quantenmechanik. ^[ref]

Expand a quantum circuit matrix element by inserting computational basis resolutions between gates, then enumerate the intermediate strings depth first. The active stack stores one basis label and accumulator per quantum circuit layer, using polynomial space for polynomially many qubits and gates. Recompute entries rather than storing an exponential matrix or state vector. The output probability requires the Born rule sum of squared amplitude moduli.

Choose an isolated pair of energy levels, with ground state $|g⟩=(0,1{)}^T$ and excited state $|e⟩=(1,0{)}^T$. Use the Pauli matrices in the ordered basis $(|e⟩,|g⟩)$, so ${\sigma }_z=\mathrm{diag}(1,-1)$. After subtracting the mean energy, prescribe the laboratory Hamiltonian operatorThe unperturbed energy gap is $\hslash {\omega }_0$, the drive has angular frequency $\omega$, and $\varphi$ fixes its oscillation phase at the chosen time origin. All of ${\omega }_0$, $\omega$, the Rabi angular frequency $\Omega$ and the Rabi detuning $\delta$ are in radians per second; ordinary frequency is angular frequency divided by $2\pi$. In particular, $\Omega$ here is the coefficient multiplying the cosine in $H_{\mathrm{lab}}/\hslash$, not twice that coefficient.

Write $|{\psi }_{\mathrm{lab}}⟩=R(t)|{\psi }_{\mathrm{rot}}⟩$ with $R(t)=\exp (-i\omega t{\sigma }_z/2)$. Transforming the Schrödinger equation gives $H_{\mathrm{rot}}=R^{†}{H}_{\mathrm{lab}}R-i\hslash R^{†}\dot{R}$. The rotating-wave approximation drops terms at angular frequency $2\omega$, leavingThis approximation requires $\Omega ,|\delta |\ll {\omega }_0,\omega$, and an interaction duration over which omitted corrections remain small. It also assumes that other energy levels can be neglected. Resonance alone does not justify either assumption. An exactly co-rotating drive has no discarded counter-rotating component; the linearly oscillating laboratory drive above does.

The Pauli matrix multiplication law gives $K^2={\Omega }_{\mathrm{eff}}^{2}I$. Separating even and odd terms of the matrix exponential therefore proveswith the continuous limit $U=I$ when $\Omega =\delta =0$. Starting from $|g⟩$, the upper probability amplitude is $-i{e}^{-i\varphi }(\Omega /{\Omega }_{\mathrm{eff}})\sin ({\Omega }_{\mathrm{eff}}t/2)$. The Born rule givesThe rotating transformation only changes the quantum phases of these basis states, so their laboratory populations are the same. Rabi detuning tilts the rotation axis of the Bloch vector: it increases the oscillation rate to ${\Omega }_{\mathrm{eff}}$ but caps the transferred population at ${\Omega }^2/({\Omega }^2+{\delta }^2)$. A fixed drive oscillation phase cancels from this single-pulse population when the initial state is $|g⟩$. It still fixes the relative quantum phase of a resulting quantum superposition and matters when another pulse supplies a phase reference.

The energy eigenspace at $E$ is the vector subspacewhere $H$ is the Hamiltonian operator and $I$ is the identity operator. It is nonzero exactly when $E$ is an energy eigenvalue. Its dimension is the multiplicity of that energy eigenvalue; degenerate energy levels have multiplicity greater than one. The ground-state subspace is ${\mathcal{E}}_{E_0}$, and its dimension is the ground-state degeneracy. A vector in an energy eigenspace need not be one of a specially chosen orthonormal basis of energy eigenstates.

Linearity makes the useful point immediate: if $H{\varphi }_1=E{\varphi }_1$ and $H{\varphi }_2=E{\varphi }_2$, then $H(a{\varphi }_1+b{\varphi }_2)=E(a{\varphi }_1+b{\varphi }_2)$. Every normalized nonzero combination stays in the same energy eigenspace. For a time-independent Hamiltonian operator, its evolution is multiplication by the common global phase $e^{-iEt/\hslash }$, so it is a stationary state. A quantum superposition within a degenerate energy eigenspace can change spatial shape when its coefficients are chosen differently, but its density does not subsequently beat under this unchanged Hamiltonian operator.

Across distinct energy eigenspaces, relative quantum phases evolve. For orthonormal eigenfunctions ${\varphi }_1,{\varphi }_2$ of the Hamiltonian operator with energy eigenvalues $E_1\ne E_2$, an equal-weight quantum superposition hasand position probability densityThe interference term can change local probabilities even though the Born rule assigns the same time-independent probability $1/2$ to each energy measurement outcome. Orthogonality makes its integral zero, preserving wavefunction normalization. This pure state is not a stationary state; some particular measurement distributions may nevertheless remain constant. An incoherent mixed state with the same energy populations has no such interference term.

For the pictured infinite square well, $\theta =3E_{1}t/\hslash$ and the interference repeats after $T=2\pi \hslash /(3E_1)$. At $t=0$, direct integration gives $⟨x⟩=L/2-16L/(9{\pi }^2)$; halfway through the period it is $L/2+16L/(9{\pi }^2)$. This is a moving expectation value, rather than a trajectory of an individual particle. The distinction between an energy eigenspace and a combination of different energy eigenspaces is what makes the different behavior possible.

Suppose a constant Hamiltonian operator has a complete discrete orthonormal basis of energy eigenstates, $H|n⟩=E_n|n⟩$. Expanding an initial pure state and applying the time-evolution operator term by term givesA projective measurement resolving these basis vectors therefore assigns the same Born rule probability $|c_n{|}^2$ to each label $n$ at every time. An energy measurement groups labels sharing the same energy eigenvalue: $P(E)={\sum }_{n:E_n=E}|c_n{|}^2$ is also constant. If $c_m,c_n\ne 0$, their probability amplitude ratio instead evolves asOnly energy differences enter this relative quantum phase. Adding a constant $\epsilon I$ to the Hamiltonian operator multiplies the entire pure state by $e^{-i\epsilon t/\hslash }$, a global phase, and leaves the density operator unchanged.

For a fixed observable $A$, the expectation value can nevertheless vary:Terms joining distinct energy eigenvalues can oscillate; diagonal terms cannot. If $[A,H]=0$, these terms between different energies vanish, so the expectation value is constant. This distinguishes conservation of energy from the stronger claim that every observable is stationary.

An energy eigenstate has only a global phase evolution and is a stationary state. A quantum superposition entirely within one degenerate energy eigenspace is also an energy eigenstate and is stationary. For a general density operator in finite dimension, stationarity under a constant Hamiltonian operator means $[H,\rho ]=0$: differentiating $U\rho U^{†}$ proves necessity, and commuting $\rho$ through the exponential proves sufficiency. Merely fixing the diagonal energy populations does not fix the off-diagonal quantum coherence.

An error syndrome is the list of outcomes obtained by measuring a chosen ordered family of stabilizer generators. Write $s_j=0$ for eigenvalue $+1$ and $s_j=1$ for eigenvalue $-1$. For a definite Pauli error $E$ on a code state, the rule isThe commuting checks admit joint orthogonal projectorsFor density operator $\rho$, the Born rule gives outcome probability $\mathrm{tr}({\Pi }_s\rho )$ and conditional state ${\Pi }_s\rho {\Pi }_s/\mathrm{tr}({\Pi }_s\rho )$ when that probability is nonzero. A definite Pauli error has one deterministic error syndrome independent of the encoded amplitudes. A coherent linear combination of Pauli errors may occupy several sectors, so measuring the error syndrome selects a sector; recovery preserves the logical qubit when the entire error family is jointly correctable. ^[ref].

An error syndrome locates an error only relative to an assumed family and a recovery rule. Two Pauli errors differing by a logical operator can share an error syndrome; see stabilizer-syndrome coset. In the three-qubit bit-flip syndrome table, $X_3$ and $X_1{X}_2$ both give $01$. Recovering with $X_3$ corrects the first but converts the second into the logical operator $X_1{X}_2{X}_3$. Likewise, $Z_1$ has error syndrome $00$ yet changes the encoded relative phase.

A physicist who developed wave mechanics. In 1926, Erwin Schrödinger made the energies of chemical atoms an eigenvalue problem, rather than prescribing a separate quantization rule for each classical orbit. He shared the Nobel Prize in Physics in 1933 with Paul Dirac.^[ref]

The Schrödinger equation turns a proposed Hamiltonian operator into predictions for a wavefunction and its evolution. Boundary conditions can select discrete energy eigenvalues, while quantum superposition makes their relative quantum phases observable through interference. The infinite square well gives a transparent worked example; a hydrogen atom supplies a physical application with a different potential energy.

The Davisson–Germer experiment gives a complementary experimental route into matter waves: an accelerated electron beam scattered from a nickel crystal produces direction-dependent collected electric current. Its apparatus and angular scans make the wave prediction testable. Interpreting a wavefunction as a probability amplitude also requires the Born rule; that statistical interpretation deserves its own history alongside Erwin Schrödinger's dynamics.

Prepare a fresh copy of the same quantum state for each trial and measure the same observable. If preparations and readouts are independent, the outcomes $X_i$ are independent and identically distributed random variables with the Born rule probability distribution. Their sample mean is an unbiased estimator of the expectation value:The law of large numbers explains convergence of the sample mean, while the standard error describes its finite-sample spread. It takes four times as many independent trials to halve that standard error. This reduces estimation error; it does not reduce the quantum uncertainty of a single prepared copy.

For the spin expectation value, let $n_{+}$ and $n_{-}$ be the two outcome counts, with $N=n_{+}+n_{-}$. ThenThe binomial distribution gives the exact sampling model. For $\theta =\pi /3$, the standard error is $\hslash \sqrt{3}/(4\sqrt{N})$: approximately $0.1083\hslash$ for $N=16$ and $0.03827\hslash$ for $N=128$. A run can fluctuate away from the predicted mean even as its typical spread decreases.

Repeatedly measuring one surviving system is a different protocol. Under the ideal Lüders rule, outcome $a_r$ leaves $P_r|\psi ⟩/\sqrt{p_r}$ when $p_r>0$. With no intervening change of observable or dynamics moving the state out of that eigenspace, the next projective measurement returns $a_r$ with certainty. Such a record is correlated and does not sample the original Born rule distribution independently. The quantum nondemolition measurement discussion describes this repeatability; fresh quantum state preparations supply the ensemble needed for the estimator above.

In the stationary-state terminology used here, an excited state is a normalized energy eigenstate with energy eigenvalue $E>E_0$, where $E_0$ is an attained ground-state energy. Its excitation cost above the ground state is $\Delta E=E-E_0>0$. Several energy eigenstates can share one excited energy eigenvalue through degenerate energy levels. An arbitrary quantum superposition with energy expectation value above $E_0$ need not be a single stationary excited state; its energy content is described by its Born rule probabilities or, for a continuum, its scalar spectral measure.

An excited state can be a stationary state: the second infinite square well mode is an immediate example. Spontaneous photon emission is a transition caused by coupling matter to the electromagnetic field; it is absent from an isolated matter-only Hamiltonian operator. The relevant energy eigenstate of that isolated model is therefore not automatically an energy eigenstate of the full interacting system. This distinction explains how an ideal stationary excited state can approximate a state with a finite experimental lifetime. See electric-dipole interaction for the coupling used in the simplest optical model.

For a one-photon transition between stationary internal states, neglecting recoil, conservation of energy requiresHere $h$ is the Planck constant and $\nu$ is the photon frequency. Energy matching alone does not guarantee a transition: in the electric-dipole interaction approximation its strength also involves the matrix element $⟨f|\mathbf{d}\cdot \mathbf{ϵ}|i⟩$, where $\mathbf{d}$ is the electric dipole moment operator and $\mathbf{ϵ}$ specifies photon polarization. A zero matrix element gives an electric-dipole selection rule. Thus an absent optical line does not prove the corresponding energy eigenvalue is absent; a different interaction can couple different states. ^[ref]. The Franck-Hertz experiment gives a particularly instructive comparison between collision excitation and photon emission.

The first excited state terminology assumes a least energy eigenvalue above $E_0$. Such a next level is not guaranteed by quantum mechanics: a continuous spectrum can start immediately above the spectral bottom, or energy eigenvalues can accumulate there. For example, a Hamiltonian operator with energy eigenvalues $0,\epsilon ,\epsilon /2,\epsilon /3,\dots$, where $\epsilon >0$, has a ground-state energy zero but no least positive energy eigenvalue: every candidate $\epsilon /n$ is exceeded downward by $\epsilon /(n+1)$. A free particle on the whole line has neither a ground state nor a first stationary excited state. Each use of a discrete excitation ladder therefore needs a specified Hamiltonian operator and its boundary conditions.

The expectation value of a quantum observable is the expected value of its measurement outcome random variable in a specified quantum state. It predicts the mean of outcomes from many identical quantum state preparations. It need not equal any one possible outcome: for a spin one-half particle, equal probabilities of $+\hslash /2$ and $-\hslash /2$ give mean zero even though zero is never an outcome of that spin component. Here $\hslash$ is the reduced Planck constant.

Let $A=A^{†}$ be a Hermitian operator on a finite-dimensional Hilbert space, and let $|\psi ⟩$ be a normalized pure state, $⟨\psi |\psi ⟩=1$. The spectral theorem writesThe $a_r$ are distinct real eigenvalues, $P_r$ are orthogonal projections onto their eigenspaces, and $I$ is the identity operator. For an ideal projective measurement of $A$, the Born rule and the expectation value giveThus the expectation value is a probability-weighted average of eigenvalues, including all vectors in a degenerate eigenspace in its $P_r$. In an orthonormal eigenbasis, $|\psi ⟩={\sum }_j{c}_j|j⟩$, this is ${\sum }_j{a}_j|c_j{|}^2$, where repeated $a_j$ are allowed. The weighted average lies between the smallest and largest eigenvalues; it can lie in a gap between them. The statistical meaning and operator expression are connected in this way in the authored treatment of average energies.^[ref]

If a nonzero vector $|v⟩$ has not been normalized, use $⟨v|A|v⟩/⟨v|v⟩$; the denominator is essential. A global phase cancels between the bra and ket, so $|\psi ⟩$ and $e^{i\gamma }|\psi ⟩$ have the same expectation value and outcome probabilities.

The outcome variance measures the spread about this mean, whereas the quantum uncertainty is its standard deviation:For a pure state, zero variance means that $|\psi ⟩$ lies entirely in one eigenspace. That eigenspace need not be one-dimensional. Knowing only a mean generally does not determine the entire outcome probability distribution.

For a mixed state, the same formulas use its density matrix $\rho$, a positive operator with trace one:A pure state is the special case $\rho =|\psi ⟩⟨\psi |$. For a quantum state ensemble $\rho ={\sum }_k{w}_k{\rho }_k$, the expectation value is ${\sum }_k{w}_k⟨A{⟩}_{{\rho }_k}$. This linearity is useful when preparations vary between trials; different quantum state ensembles can have the same density matrix.

These formulas require no operator-domain qualifications in finite dimension. For an unbounded self-adjoint operator, the spectral theorem instead gives a spectral probability measure; a finite mean requires an integrable absolute first moment, and finite variance requires a finite second moment. Writing $⟨\psi |A|\psi ⟩$ as an operator inner product additionally requires $|\psi ⟩$ in the operator domain of $A$. The quadratic form of a positive quantum Hamiltonian explains the useful wider form-domain version.

Keep the first pulse's oscillation phase zero and give the second phase $\phi$ in the Driven two-level Rabi model. Its upper off-diagonal Hamiltonian operator entry is $\hslash \Omega e^{-i\phi }/2$. Multiplying the two pulse unitary operators and the free-flight unitary operator givesThe Born rule gives the displayed phase-dependent form using the $p,b,\theta$ of the Ramsey fringe envelope. Thus $\phi =0$ reproduces the existing expression, while $\phi =\pi$ turns a resonant transfer maximum into zero transfer. A single pulse's population is insensitive to its drive phase; the second coherent interaction makes their difference observable. An uncontrolled, uniformly random $\phi$ instead averages this probability to $2p(1-p)$, leaving the broad pulse response but removing the dark-flight fringes.

Finite pulses also contribute to the near-resonant frequency slope. For $\Omega \tau =\pi /2$, differentiating $\theta$ at $\delta =0$ gives ${\theta }^{\prime }(0)=1/\Omega$. Consequently the phase near resonance isAt $\phi =\pi /2$ the exact resonant slope is $\partial P/\partial \nu =-\pi T_{\mathrm{eff}}$. For the plotted parameters $T_{\mathrm{eff}}\simeq 5.637\mathrm{ms}$; the near-resonant estimate $1/(2T_{\mathrm{eff}})\simeq 88.71\mathrm{Hz}$ explains why the exact finite-pulse width below differs from $100\mathrm{Hz}$. The slope is exact at resonance under these assumptions, while this width estimate uses the local phase expansion. A velocity distribution requires averaging the full response, not substituting one effective flight time.