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The lowest singlet state isFor the lowest triplet states take $\lambda =\pm 1$ and $m_s=-1,0,1$:orthogonality of $u_0$ and $u_{\lambda }$ verifies wavefunction normalization of the antisymmetric spatial factor. At this same energy there are also two excited singlet states, obtained by replacing its minus sign with a plus sign and the spin factor by $|0,0⟩$. Together they reproduce the eight states counted in part a.

For independent angular momenta ${\mathbf{J}}_1,{\mathbf{J}}_2$, set $\mathbf{J}={\mathbf{J}}_1+{\mathbf{J}}_2$. Since different subsystems commute, $\mathbf{J}$ satisfies the same angular-momentum algebra. The product basis $|j_1{m}_1⟩|j_2{m}_2⟩$ diagonalizes $J_1^2,J_2^2,J_{1z},J_{2z}$; the coupled basis diagonalizes $J_1^2,J_2^2,J^2,J_z$. Its labels obeyThe Clebsch-Gordan coefficients are the unitary change of basis between them. Start from the maximum-weight state $j=j_1+j_2,m=j$, apply $J_{-}=J_{1-}+J_{2-}$ with wavefunction normalization, and construct the remaining multiplets by orthogonality.

For two spin-one-half systems, the symmetric triplet state is $|\uparrow \uparrow ⟩$, $(|\uparrow \downarrow ⟩+|\downarrow \uparrow ⟩)/\sqrt{2}$, $|\downarrow \downarrow ⟩$, with $j=1$; the antisymmetric singlet state $(|\uparrow \downarrow ⟩-|\downarrow \uparrow ⟩)/\sqrt{2}$ has $j=0$. The dimension identity ${\sum }_j(2j+1)=(2j_1+1)(2j_2+1)$ checks completeness. Coupling orbital and intrinsic spin similarly gives total atomic angular momentum and organizes spin-orbit energy splittings. Exchange symmetry is an additional restriction when the constituents are identical.

The populations giveTogether with $⟨S_y⟩=(\hslash /2)\sin (\Omega t)$, this describes Larmor precession of a spin initially perpendicular to the field. The positive angular frequency is $|\Omega |$; the sign specifies the rotation sense through $d⟨\mathbf{S}⟩/dt=\gamma ⟨\mathbf{S}⟩\times \mathbf{B}$. The factor of two between the spinor amplitudes and the measured spin is essential. The model with quantum coherence predicts no decay; spin relaxation or dephasing in a real solid can damp the oscillation.

Write $\gamma =ge/(2m)$, retaining the printed magnetic moment convention. The displayed two-dimensional matrices are Pauli matrices, and the spin Hamiltonian operator isFor an x-directed field let $\omega =\gamma B_x/2$. The Schrödinger equation gives $i{\dot{c}}_{+}=-\omega c_{-}$ and $i{\dot{c}}_{-}=-\omega c_{+}$. With $c_{+}(0)=1,c_{-}(0)=0$, these equations yieldEquivalently, $U(t)=e^{i\omega t{\sigma }_x}=I\cos \omega t+i{\sigma }_x\sin \omega t$. If $e$ denotes a positive elementary charge magnitude, a free electron is conventionally assigned a minus sign in its magnetic moment; that alternative reverses the rotation sense. The expressions here consistently use the moment specified in the paper.

Put $\kappa =e^2/(4\pi {ϵ}_0)$. Substitution of $\psi =R(r)\Phi (\varphi )$ into the time-independent Schrödinger equation, followed by division by $R\Phi$ and multiplication by $r^2$, separates the angular dependence:Thus $\Phi =e^{im\varphi }/\sqrt{2\pi }$ andThe single-valued wavefunction condition, $\Phi (\varphi +2\pi )=\Phi (\varphi )$, requires $m\in \mathbb{Z}$. The regular boundary condition at the origin selects $R\sim r^{|m|}$. Accordingly use $s=|m|$ in the radial ansatz; the printed $x^m$ notation describes the $m\ge 0$ representatives.

For the two-dimensional Coulomb bound state, substitution of $R=x^s{e}^{-x/2}G$ with the stipulated radial and energy scales givesThe coefficient of $x^n$ in the power series isThe regular solution otherwise has an exponentially growing contribution at large $x$, incompatible with being normalizable. Termination at degree $n_r\ge 0$ therefore requiresThe resulting $G$ is proportional to a Generalized Laguerre polynomial.

Define $R_{\mathrm{y}}=\mu {\kappa }^2/(2{\hslash }^2)$, the hydrogenic Rydberg energy for the stipulated mass. The first three distinct two-dimensional energies are $-4R_{\mathrm{y}},-4R_{\mathrm{y}}/9,-4R_{\mathrm{y}}/25$, whereas in three dimensions they are $-R_{\mathrm{y}},-R_{\mathrm{y}}/4,-R_{\mathrm{y}}/9$. Both series approach zero from below, but the planar ground state is four times more tightly bound. Without spin the respective quantum degeneracies are $1,3,5$ and $1,4,9$; if individual degenerate states are counted, the second and third planar states already share the first excited energy. This comparison retains the supplied $1/r$ interaction; it does not replace it by the logarithmic electrostatic potential of a genuinely two-dimensional electromagnetic theory.

identical particles have the same intrinsic properties. Exchanging their bookkeeping labels cannot distinguish a physical preparation or change a measurable prediction. This is stronger than merely failing to track classical trajectories. For ordinary bosons and fermions, the many-particle wavefunction has respectively bosonic exchange symmetry or fermionic exchange symmetry under every particle exchange operator, acting on spatial and spin coordinates together. The Spin-statistics theorem connects integer spin to bosons and half-integer spin to fermions; this connection uses relativistic quantum-field assumptions, rather than following from the nonrelativistic Schrödinger equation alone.

For one-particle states $u,v$ satisfying orthonormality, the two alternatives form a quantum superposition:Its probability density contains an exchange interference term, absent from an incoherent mixture of labelled alternatives. The antisymmetric expression vanishes when both one-particle states are identical: one complete one-particle state can contain at most one fermion. This Pauli exclusion principle explains electron shell filling, the electronic Fermi sea and degeneracy pressure. Opposite spins are different one-particle states, so two electrons may share an atomic orbital. Spatially separated wave packets with negligible overlap can often be treated as distinguishable for local measurements; the underlying exchange symmetry remains.

In thermal equilibrium, occupation of a level of energy $ϵ$ obeysbosons can accumulate macroscopically in one state, giving Bose-Einstein condensation; fermions instead fill successive states up to the Fermi energy at zero temperature. When occupation is dilute, both expressions reduce to the Maxwell-Boltzmann distribution. The identical-particle classical partition function contains $1/N!$, avoiding spurious entropy from permutations and the Gibbs paradox. Exchange effects become conspicuous when the thermal de Broglie wavelength is comparable to the interparticle spacing.

An operational test is the Hong-Ou-Mandel effect. Down-converted photon pairs enter separate ports of a balanced beam splitter; indistinguishable alternatives for one photon per output cancel. Scanning the relative arrival delay restores coincidences away from overlap. Matching polarization, spectral filtering and spatial alignment controls distinguishability; measuring delayed accidental coincidences controls background. The observed dip tests two-photon interference, and its finite depth must not automatically be interpreted as a failure of bosonic symmetry. The original apparatus varied beam-splitter position and subtracted a separately measured accidental background.^[ref]

Addition of two spin-one-half angular momenta gives total spin $S=0$ or $S=1$. The normalized singlet state and triplet states areThey have $S^2$ eigenvalues $0$ and $2{\hslash }^2$, and $S_z=M\hslash$. The singlet state is antisymmetric under a particle exchange operator, whereas all three triplets have symmetric spin-exchange parity. For two identical electrons the full state must be antisymmetric: a singlet state pairs with a spatial state with symmetric exchange parity, a triplet state with an antisymmetric spatial state. Thus two electrons in the same atomic orbital must form a singlet state.

The identity ${\mathbf{S}}_1\cdot {\mathbf{S}}_2=(S^2-S_1^2-S_2^2)/2$ gives $-3{\hslash }^2/4$ in the singlet state and $+{\hslash }^2/4$ in the triplet state. Hence an exchange interaction distinguishes their energies, with ordering determined by its coupling sign. The singlet state has perfect opposite-spin correlations along any common measurement axis and is entangled. The $M=0$ triplet state is also entangled, while the $M=\pm 1$ triplet states are product states along the chosen axis.

For observables with finite variances, the Heisenberg uncertainty principle gives $\Delta A\Delta B\ge |⟨[A,B]⟩|/2$; in particular $\Delta x\Delta p\ge \hslash /2$. It concerns the spreads of measurements in a prepared state, rather than only disturbance by a measuring device. Identical integer-spin particles have symmetric full states and Bose-Einstein statistics; half-integer-spin particles have antisymmetric full states and Fermi-Dirac statistics. The latter imply Pauli exclusion from one complete single-particle state, including spin.

Inside an infinite square well, solutions satisfying both zero boundary conditions arewith zero wavefunction outside. For the ground state, direct integration givesThe infinite-well ground-state uncertainty product follows:The ground state is not a minimum-uncertainty Gaussian. Here momentum variance is the usual kinetic-momentum second moment of the confined state; the hard-wall momentum operator has domain subtleties that do not alter this kinetic-energy result.

For spin degeneracy in filling a one-dimensional well, let $E_1={\pi }^2{\hslash }^2/(2m{L}^2)$ and assume the spin levels are degenerate and available. Four spin-zero bosons all occupy the lowest orbital, giving $4E_1$. Four spin-$1/2$ fermions fill two spin states in each of $n=1,2$, giving $10E_1$. Spin-$3/2$ fermions have four spin projections, so all four can occupy $n=1$ in different complete states, giving $4E_1$. These fillings do not impose full spin polarization.

matrix multiplication gives ${\sigma }_i{\sigma }_j={\delta }_{ij}I+i{ϵ}_{ijk}{\sigma }_k$, hence $[{\sigma }_i,{\sigma }_j]=2i{ϵ}_{ijk}{\sigma }_k$. For physical neutron spin, use $\mathbf{S}=(\hslash /2)\mathbf{\sigma }$, so $[S_i,S_j]=i\hslash {ϵ}_{ijk}{S}_k$, $S^2=3{\hslash }^2/4$, and measurement along any axis gives $\pm \hslash /2$.

For the specified field, $H=(\alpha B\hslash /2){\sigma }_y$. The Time-dependent Schrödinger equation is $i\hslash \dot{\psi }=H\psi$ with $\psi (0)=(1,0{)}^T$. The uniform-field spin precession follows from ${\sigma }_y^2=I$:

The sign of the precession is contained in the given $\alpha$. The normalized $x$-axis eigenstates are $(1,1{)}^T/\sqrt{2}$ and $(1,-1{)}^T/\sqrt{2}$.

The measurement direction is $\mathbf{n}=(0,\sin \theta ,\cos \theta )$, as confirmed by the original diagram. Write $c=\cos (\theta /2)$ and $s=\sin (\theta /2)$. The spinors ${\chi }_{+}=(c,is{)}^T$ and ${\chi }_{-}=(is,c{)}^T$ have unit norm and inner product $ics-isc=0$. Applying $\mathbf{n}\cdot \mathbf{\sigma }$ gives eigenvalues $+1$ and $-1$. At $\theta =0$ they are the usual $z$ basis; at $\pi /2$ they are the $y$ basis up to a phase; at $\pi$ the $z$ up/down roles are exchanged, with a factor $i$; and at $2\pi$ both return with a minus sign. A spinor changes sign under a full rotation, while its isolated-state measurement probabilities are unchanged.

For spin measurement in the yz plane, projection givesFor $\theta =0$ these are ${\cos }^2\varphi ,{\sin }^2\varphi$; for $\pi /2$ both are $1/2$ at all times; for $\pi$ they are exchanged; and for $2\pi$ they are the same as at zero angle. The constant $y$ probabilities also follow from conservation of $S_y$.

angular momentum generates rotations. Its components obey $[J_i,J_j]=i\hslash {ϵ}_{ijk}{J}_k$, and $J^2$ commutes with each component. A compatible basis has $J^2={\hslash }^{2}j(j+1)$ and $J_z=m\hslash$, where $m=-j,-j+1,\dots ,j$. ladder operators change $m$ by one, terminate at $\pm j$, and give $2j+1$ magnetic substates. Different Cartesian components generally cannot all be sharp simultaneously.

orbital angular momentum is $\mathbf{L}=\mathbf{r}\times \mathbf{p}=-i\hslash \mathbf{r}\times \nabla$. Its angular eigenfunctions are spherical harmonics, with integer $\ell$ arising from their spatial rotation properties and single-valuedness. spin is intrinsic angular momentum, not literal rotation of a finite charged sphere. It may be half-integer; spin $1/2$ is represented by $\mathbf{S}=\hslash \mathbf{\sigma }/2$. For several contributions, $\mathbf{J}=\mathbf{L}+\mathbf{S}$ obeys the same algebra. Coupling angular momenta $j_1,j_2$ permits $J=|j_1-j_2|,\dots ,j_1+j_2$, with Clebsch-Gordan coefficients relating product and coupled bases. spin-orbit coupling can distinguish these total-angular-momentum sectors.

The Stern-Gerlach apparatus sends a collimated neutral atomic beam through an inhomogeneous magnetic field and records its deflection. A magnetic moment experiences $F_z\simeq {\mu }_z\partial B_z/\partial z$; field uniformity would produce precession but no analogous net separating force. A classically continuous distribution of moment orientations would broaden the beam continuously. Gerlach and Stern instead observed separated silver-beam components. Reversing or removing the field and comparing the undeflected profile controls the magnetic origin; collimation, velocity spread and finite resolution affect the spots. The original experiment demonstrated space quantization; its modern silver interpretation uses the unpaired electron spin with nearly zero orbital angular momentum, rather than a direct measurement of a free electron's trajectory.^[ref]

For two spin-$1/2$ particles, the triplet state sector has $S=1$ and symmetric spin statesThe spin singlet state has $S=0$ and antisymmetric spin stateTheir total $S^2$ values are $2{\hslash }^2$ and zero, while ${\mathbf{S}}_1\cdot {\mathbf{S}}_2$ has values ${\hslash }^2/4$ and $-3{\hslash }^2/4$. The singlet is rotationally invariant and gives anticorrelated spin measurements along a common axis. For identical fermions the complete state is antisymmetric: a symmetric spatial state pairs with a singlet spin state, whereas an antisymmetric spatial state pairs with triplet spin. Orbital, spin and coupled angular momenta share an algebra, but their physical origins and allowed representations differ.

The remaining cyclic commutators are $[S_y,S_z]=i\hslash S_x$ and $[S_z,S_x]=i\hslash S_y$. In a spin-$s$ irreducible representation,For spin one-half, $S_i=\hslash {\sigma }_i/2$, appropriate to an electron's spin. Each $S_i^2={\hslash }^{2}I/4$, so this Hamiltonian is $H=A{\hslash }^{2}I/4$. The orthonormal vectors $(1,0{)}^T$ and $(0,1{)}^T$ are eigenstates with the same energy $A{\hslash }^2/4$; every normalized superposition is also an eigenstate. The $B$ term vanishes identically because spin-one-half quadratic anisotropy is constant.

For the supplied three-dimensional basis one consistent choice isThese Hermitian matrices obey the cyclic commutators with the given $S_x$, and $S^2=2{\hslash }^{2}I$, representing spin one. Their squares giveThus the three normalized Cartesian basis vectors $e_1,e_2,e_3$ have energies ${\hslash }^2(A-B)$, ${\hslash }^2(A+B)$ and $0$, respectively; degeneracies permit arbitrary orthonormal choices in the corresponding eigenspaces.

The parallel and antiparallel $S_x$ states are $|+x⟩=(0,1,-i{)}^T/\sqrt{2}$ and $|-x⟩=(0,1,i{)}^T/\sqrt{2}$. Evolution from the first givesThis spin-one reversal under quadratic anisotropy is complete whenprovided $A+B\ne 0$. If $A+B=0$, its initial state is stationary up to phase and complete reversal never occurs. Assume real $A,B$ for a Hermitian Hamiltonian.

The anisotropic quantum harmonic oscillator is a sum of three commuting one-coordinate oscillator Hamiltonians. Substituting $\psi =X(x)Y(y)Z(z)$ and dividing by $XYZ$ gives a sum of three functions of independent coordinates, so each equals a separation constant. ConsequentlyFor a time-independent operator, conservation for arbitrary states follows from $[H,Q]=0$, since $d⟨Q⟩/dt=(i/\hslash )⟨[H,Q]⟩$. The first labelled operator is $i{L}_z/\hslash$; the second is $-L^2/{\hslash }^2$. The kinetic energy is rotationally invariant. The potential is invariant under rotations about $z$ precisely when (i) ${\omega }_x^2={\omega }_y^2$; full rotational invariance requires (ii) ${\omega }_x^2={\omega }_y^2={\omega }_z^2$. For positive oscillator frequencies these are equality of the frequencies themselves. Acting with the commutators on arbitrary test functions excludes anisotropic potentials in case (ii).

In the isotropic case let $b=m\omega /\hslash$. ThenThe polynomial $x$ is the first excited oscillator factor and the other two factors are ground-state Gaussians. The first excited spatial level has three independent choices, proportional to $x,y,z$. Odd parity gives $⟨x⟩=0$, and Gaussian integration yieldsFor oscillator uncertainty and allocation of classical energy, the $x$ mode has energy $3\hslash \omega /2$, whose classical amplitude is $A_x=\sqrt{3\hslash /(m\omega )}$, giving $\Delta x=A_x/\sqrt{2}$. If “same energy” instead means assigning the entire three-dimensional energy $5\hslash \omega /2$ to one classical coordinate, its amplitude is $\sqrt{5\hslash /(m\omega )}$ and the ratio is $\sqrt{3/10}$. A general three-dimensional classical orbit's $x$ amplitude is not fixed by total energy without specifying its allocation among modes.

The capacity of an isotropic oscillator shell, including the two electron spin states, is $(N+1)(N+2)$ electrons. Nine non-interacting electrons occupy shells as $2,6,1$ for $N=0,1,2$. ThusThe least positive excitation promotes an electron by one oscillator quantum. Rearrangements within the partly filled degenerate shell remain ground states and cost no energy.

Write the one-electron Coulomb energies as $E_n=-C/n^2$, $C>0$. The Pauli exclusion principle allows $2n^2$ electrons in shell $n$, including spin. The ground configuration therefore has two electrons in $n=1$ and seven in $n=2$, giving $E_g=-C(2+7/4)=-15C/4$. The least energy-increasing promotion is from $n=2$ to $n=3$:Rearranging the partly occupied degenerate $n=2$ shell does not produce a higher energy. Both total energies are negative, so this ratio is below one even though $E_e>E_g$.

electron spin is intrinsic angular momentum, independent of an orbital wavefunction's $\mathbf{r}\times \mathbf{p}$. It has $s=1/2$, soA spatial orbital therefore carries a two-component spinor degree of freedom. Noncommuting components do not describe an ordinary vector with simultaneously definite projections; measurements along one axis give only the two allowed values. Even a spherically symmetric $l=0$ orbital retains electron spin.

The associated magnetic moment is $\mathbf{\mu }=-g_{e}e\mathbf{S}/(2m_e)$ with $e>0$ and $g_e\simeq 2$. A spinor changes sign under a $2\pi$ rotation and returns under $4\pi$; that sign is observable only relative to another coherent amplitude, not as an isolated global phase. A literal classically rotating charged sphere does not account for this fixed half-integer representation, component algebra and spinor rotation law. Classical angular momentum provides useful analogies for torque and precession, but no ordinary classical orientation reproduces the full intrinsic quantum spin structure.

Expanding with the angular momentum commutators givesFor ${\hat{L}}_z|\psi ⟩=\alpha \hslash |\psi ⟩$, commuting ${\hat{L}}_z$ past a ladder operator givesThus the raised or lowered vector, if nonzero, is an eigenvector with the shifted eigenvalue; an angular momentum ladder endpoint can instead be annihilated. Also $[{\hat{L}}^2,{\hat{L}}_{\pm }]=0$, so ${\hat{L}}^2{\hat{L}}_{\pm }|\psi ⟩=\Lambda {\hslash }^2{\hat{L}}_{\pm }|\psi ⟩$ for every nonzero ladder result.

For orbital angular momentum, ${\hat{L}}_z=-i\hslash {\partial }_{\varphi }$ gives an azimuthal factor $e^{i\alpha \varphi }$. Single-valuedness under $\varphi \mapsto \varphi +2\pi$ requires integer $\alpha$. Positivity of ladder norms givesfor normalized states. A fixed finite $\Lambda$ therefore has upper and lower endpoints. Writing the upper endpoint as $m=\ell$, its vanishing raising norm gives $\Lambda =\ell (\ell +1)$; the lower endpoint is $m=-\ell$. Consequentlywith $\ell =0,1,2,\dots$. This integer conclusion is for orbital angular momentum; spin representations can also have half-integer labels.

For the specified Gaussian-radial state, use a Cartesian p-orbital decomposition: write $x+y+z=r(\sin \theta \cos \varphi +\sin \theta \sin \varphi +\cos \theta )$. Its angular factor isOnly $\ell =1$ occurs. The squared angular coefficients are $2,2,2$ before common normalization, so each allowed $m$ has probability one third. Therefore the simultaneous outcome isThe common normalized radial factor cancels from this ratio. The standard symmetric $m$ sequence used above resolves the duplicated central positive entry in the printed list.

Direct matrix multiplication givesThe normalized $S_x$ eigenvectors are $(|\uparrow ⟩\pm |\downarrow ⟩)/\sqrt{2}$, and the $S_y$ eigenvectors are $(|\uparrow ⟩\pm i|\downarrow ⟩)/\sqrt{2}$, with eigenvalues $\pm \hslash /2$ in each case.

For $N=|a{|}^2+|b{|}^2>0$, allowing for a possibly unnormalized input pair of coefficients,For a normalized state $N=1$. The second result follows because each squared Spin operator matrix equals ${\hslash }^2\hat{I}/4$.

The tilted component is ${\hat{S}}_{z^{\prime }}=(\hslash /2)\left(\begin{array}{cc}\cos \theta & \sin \theta \\ \sin \theta & -\cos \theta \end{array}\right)$. Its eigenvalues remain $\pm \hslash /2$, with one real phase convention for the normalized eigenvectorsProjecting the initial $|\uparrow ⟩$ onto them gives $P_{+}={\cos }^2(\theta /2)$ and $P_{-}={\sin }^2(\theta /2)$. ThusA smaller expectation does not imply a smaller individual spin eigenvalue; it describes the probabilities of the same two measurement outcomes.

identical particles have the same intrinsic properties, including mass, charge and spin. Their labels are bookkeeping devices rather than measurable identities. When wave functions overlap, quantum mechanics supplies no observable trajectory that permanently identifies “particle 1” independently of “particle 2”. A many-particle description must therefore treat exchange consistently. The Hamiltonian and physical observables are invariant under relabelling identical particles.

For two particles, the exchange operator obeys ${\hat{P}}_{12}^2=\hat{I}$. The usual three-dimensional symmetrization postulate selects states symmetric under exchange for bosons and antisymmetric for fermions. In relativistic quantum theory, the Spin-statistics theorem associates integer spin with bosons and half-integer spin with fermions under its locality and positivity assumptions; the connection is not derived merely from ${\hat{P}}_{12}^2=\hat{I}$ in elementary nonrelativistic mechanics. For orthonormal one-particle states $u$ and $v$, the two-particle spatial combinations areThe sign concerns the complete state, including spin and other internal variables, not necessarily the spatial factor alone.

The antisymmetric state vanishes if both fermions occupy the same one-particle state: this is the Pauli exclusion principle. For $N$ fermions in orthonormal spin orbitals ${\chi }_j$, the normalized Slater determinant $\Psi =(N!{)}^{-1/2}\det [{\chi }_j(i)]$ supplies the required exchange sign. Bosonic occupation has no corresponding upper limit, and symmetrized products describe many bosons. Fermionic occupation is zero or one per complete one-particle state; two electrons can still occupy the same spatial atomic orbital with opposite spin.

Spin and spatial symmetry are linked. A two-electron spin singlet state is antisymmetric, so its spatial factor must be symmetric. A symmetric triplet state instead requires an antisymmetric spatial factor. Exchange then changes pair correlations and the energies available when interactions depend on particle separation, even without introducing a new classical “exchange force”. It contributes to atomic shell structure, bonding and magnetic behaviour.

In an occupation-number description, bosonic creation and annihilation operators satisfy $[{\hat{a}}_i,{\hat{a}}_j^{†}]={\delta }_{ij}$, whereas fermionic operators satisfy $\{{\hat{c}}_i,{\hat{c}}_j^{†}\}={\delta }_{ij}$ and anticommute among themselves. The latter imply $({\hat{c}}_i^{†}{)}^2=0$. This formalism implements the same exchange constraints without assigning permanent particle labels.

For noninteracting particles in thermal equilibrium, the mean occupation of a state of energy $ϵ$ isFermi-Dirac statistics produces a filled Fermi sea at zero temperature and degeneracy pressure; Bose-Einstein statistics permits macroscopic Ground state occupation when the density of available states and thermodynamic conditions allow condensation. The different statistics therefore have measurable collective consequences, not just different notation.^[ref]

When phase-space occupation is dilute, both distributions reduce to the Maxwell–Boltzmann statistics limit. Likewise, well-separated localized wave packets have negligible overlap and small exchange corrections, so effectively labelled classical trajectories can become a useful approximation. In two spatial dimensions more general exchange statistics are possible; the standard boson/fermion account here concerns ordinary three-dimensional particles and their total states.

For the nonrelativistic Coulomb Hamiltonian with reduced electron-proton mass $\mu$, separation in Spherical coordinate system gives ${\psi }_{n\ell m}(r,\theta ,\varphi )=R_{n\ell }(r)Y_{\ell m}(\theta ,\varphi )$. The quantum numbers obey $n\ge 1$, $0\le \ell \le n-1$ and $-\ell \le m\le \ell$. These are joint eigenstates of energy, $L^2$ and $L_z$, with the latter two eigenvalues $\ell (\ell +1){\hslash }^2$ and $m\hslash$.

The Coulomb bound-state energies and characteristic length areFor example, ${\psi }_{100}=(\pi a_{\mu }^3{)}^{-1/2}{e}^{-r/a_{\mu }}$ is spherically symmetric and has no radial node. In general the radial part contains an exponential times a Generalized Laguerre polynomial, with $n-\ell -1$ radial nodes. The spherical harmonic specifies angular structure and azimuthal phase; real linear combinations of degenerate $m$ states give familiar directional orbitals.

The leading Coulomb energy depends on $n$ alone, giving $n^2$ spatial states for each principal shell, or $2n^2$ including electron spin. Fine structure, Lamb shift and Hyperfine structure lift parts of this ideal degeneracy. An atomic orbital is a probability amplitude, not a classical planetary path.^[ref]

Reduced radial equation. A spherical harmonic satisfies ${\hat{L}}^2{Y}_{\ell m}=\ell (\ell +1){\hslash }^2{Y}_{\ell m}$. Substitute $\psi =R{Y}_{\ell m}$ into the time-independent Schrödinger equation, divide out the angular function, and put $R=U/r$. Direct differentiation givesMultiplication by $r$ then gives the Radial Schrodinger equationHere $\mu =m_1{m}_2/(m_1+m_2)$ is the reduced mass, and the extra positive term is the centrifugal potential.

Boundary conditions. At the origin this finite central potential has no point interaction. The physical radial solution is regular there, requiring $U(0)=0$; for $\ell =0$, a nonzero constant $U(0)$ would give $R\sim 1/r$ and a point-source singularity of the three-dimensional Laplacian. Mere square integrability alone would not remove that singular solution. For a bound state, the radial probability integral is ${\int }_0^{\infty }|U{|}^{2}dr$, so the exterior solution must decay and $U(r)\to 0$ as $r\to \infty$.

Solutions for zero orbital angular momentum. For $\ell =0$ and $-V_0<E<0$, defineThe interior equation is $U^{\prime \prime }+k^{2}U=0$; $U(0)=0$ excludes the cosine. The exterior equation is $U^{\prime \prime }-q^{2}U=0$; normalizability excludes the growing exponential. ThusThe constants cannot remain independent once the interface is matched. Since the potential step is finite, both $U$ and $U^{\prime }$ are continuous at $a$:Dividing the equations yields

Existence and number of s-wave bound states. Put $z=ka$, $y=qa$, and ${\rho }_0=a\sqrt{2\mu V_0}/\hslash$. ThenThe lowest branch lies on $\pi /2<z<\pi$. Along it, $y=-z\cot z>0$ and ${\rho }_0=z/\sin z$ increases continuously from $\pi /2$ to infinity. Therefore a first negative-energy solution exists precisely when ${\rho }_0>\pi /2$, orFurther branches begin at $z=3\pi /2,5\pi /2,\dots$ as $q\to 0^{+}$. Hence the bound-state thresholds of a spherical square well give exactly one negative-energy $\ell =0$ state whenThe upper equality is included: the second branch is then only at $E=0$, with constant exterior $U$, and is not normalizable. If threshold cases are excluded by convention, the commonly quoted open interval has a strict upper inequality; the physical negative-energy state count at equality is still one.

Deuteron estimate. Using $m_p{c}^2\simeq 938.27\mathrm{MeV}$, $m_n{c}^2\simeq 939.57\mathrm{MeV}$ and $\hslash c\simeq 197.327\mathrm{MeV}\mathrm{fm}$ gives $\mu c^2\simeq 469.46\mathrm{MeV}$. At $a=2.1\mathrm{fm}$,The threshold for a second $s$ state is $9V_{\ast }\simeq 209\mathrm{MeV}$, far above the stipulated depth $33.5\mathrm{MeV}$. Thus this model has no radially excited s-wave bound state.

Checking other orbital angular momentum sectors matters before ruling out every excitation. At the first $p$-wave threshold, the regular interior reduced radial function is $r{j}_1(kr)$ and the zero-energy exterior function is proportional to $r^{-1}$. Matching their logarithmic derivatives requires $j_0(ka)=0$, whose first root is $ka=\pi$. HenceLarger $\ell$ only increases the centrifugal potential. Therefore no bound orbital excited states are expected in the specified central square-well model. Its spin dependence and tensor nuclear forces have not been specified; the calculation does not resolve the real deuteron's internal spin structure.

Distinguishable noninteracting particles. Interpret $V$ as the same external one-particle potential for each particle; the total potential is $V({\mathbf{r}}_1)+V({\mathbf{r}}_2)$. The Time-dependent Schrödinger equation isLet $\hat{h}{\varphi }_a={ϵ}_a{\varphi }_a$ and $\hat{h}{\varphi }_b={ϵ}_b{\varphi }_b$, where $\hat{h}=-{\hslash }^2{\nabla }^2/(2m)+V$. Applying ${\hat{h}}_1+{\hat{h}}_2$ to the product multiplies it by ${ϵ}_a+{ϵ}_b$. The time derivative of $e^{-iEt/\hslash }$ multiplies it by $E$. Thus the proposed stationary product is a solution providedThe tensor product separates the two independent one-particle dynamics.