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Use $[x,p]=i\hslash$. Acting on a smooth test wavefunction, $[f(x),p]\psi =f(-i\hslash {\psi }^{\prime })+i\hslash (f\psi {)}^{\prime }=i\hslash f^{\prime }\psi$. Take $f$ real and use the self-adjoint operator domain with vanishing integration-by-parts boundary terms. Writing $Q=p-if$ givesThe energy form is $⟨\psi ,H\psi ⟩=\Vert Q\psi {\Vert }^2/(2m)\ge 0$, so every normalizable energy eigenstate has $E\ge 0$. If a normalizable zero-energy state exists, its nonnegative norm must vanish, $Q{\psi }_0=0$. HenceZero energy is an additional existence assumption, not a consequence of factorization alone.

For ${\psi }_1=Q^{†}{\psi }_0$, the commutator $[Q,Q^{†}]=2\hslash f^{\prime }$ givesThus $\alpha (x)=-i{\hslash }^2{f}^{\prime \prime }(x)/m$ and $\beta (x)=\hslash f^{\prime }(x)/m$ in the requested relation. Generally these are multiplication functions, not constant coefficients, and ${\psi }_1$ is not automatically an energy eigenstate.

If $f(x)=c{x}^n+\cdots$, its integral has leading term $c{x}^{n+1}/(n+1)$. Decay at both infinities on the full real line requires odd $n$ and positive leading coefficient $c$. Odd degree alone is not sufficient. For $f=kx$ take $k=m\omega >0$. Then $H=H_{\mathrm{SHO}}-\hslash \omega /2$, $\alpha =0$ and $\beta =\hslash \omega$. After normalization and removal of an irrelevant phase,The corresponding factorized-Hamiltonian energies are zero and $\hslash \omega$; the constant shift must be restored for the stated oscillator Hamiltonian.

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]

Use the canonical commutation relations $[\hat{x},{\hat{p}}_x]=[\hat{y},{\hat{p}}_y]=i\hslash$, with cross-coordinate commutators zero. For either coordinate,Thus $2\alpha \beta \hslash =1$. To obtain the required Hamiltonian, the ratio of its position operator and momentum operator coefficients must be preserved:where the positive root follows from the requested signs. ConsequentlyThe annihilation operators are dimensionless; $\alpha$ has units of inverse length and $\beta$ has units of inverse momentum. Operators belonging to different coordinates commute automatically. Writing the number operators as ${\hat{N}}_j={\hat{a}}_j^{†}{\hat{a}}_j$, substitution givesThe constant is the sum of the two zero-point energies of this two-dimensional isotropic harmonic oscillator.

For a particle in a ring, the arc-length coordinate is $s=R\varphi$. The tangential kinetic energy isThe constraint removes radial motion; the constant potential energy along the ring can be chosen as zero. The tangential momentum operator is ${\hat{p}}_s=-i\hslash {\partial }_s$, or equivalently the angular momentum operator is ${\hat{L}}_z=-i\hslash {\partial }_{\varphi }$. ThusIts physical domain has periodic boundary conditions, $\psi (\varphi +2\pi )=\psi (\varphi )$ and ${\psi }^{\prime }(\varphi +2\pi )={\psi }^{\prime }(\varphi )$. These make the Hamiltonian self-adjoint and reflect that $\varphi$ and $\varphi +2\pi$ describe the same point. No magnetic flux or additional angle-dependent potential energy is present.

Identical spin one-half particles are fermions. By fermionic exchange symmetry, the complete spatial-and-spin wavefunction must change sign when the two particle labels are exchanged. Define the normalized antisymmetric spin-one-half singlet stateand the three symmetric spin-one-half triplet statesThe Hamiltonian is independent of spin, so these spin functions carry no additional energy.

Both particles can occupy $u_0$ if their spin factor is antisymmetric. The unique ground state wavefunction isTwo equal-spin particles could not share this orbital, by the Pauli exclusion principle.

At the first excited energy, $E=ϵ={\hslash }^2/(2m{R}^2)$, one orbital is $u_0$ and the other is $u_s$ with $s=+1$ or $-1$. Define symmetric and antisymmetric normalized spatial functionsFor each $s$, all allowed wavefunctions are spanned byThere are $2(1+3)$ orthonormal states, hence first-excited-state degeneracy $g=8$. In each product, exactly one factor is antisymmetric, ensuring the required total fermionic exchange symmetry.

Time dependence in quantum mechanics describes how a prepared quantum state changes and thereby changes the probabilities of later measurements. For an isolated system, the Schrödinger picture assigns this evolution to a state vector $|\psi (t)⟩$, governed by the Time-dependent Schrödinger equationThe Hamiltonian is a self-adjoint operator; it has units of energy, while $\hslash$ has units of action, so $\hat{H}/\hslash$ has units of inverse time. For a particle with potential energy $V(\mathbf{r},t)$, this becomesGiven a suitable initial wavefunction and the physical boundary conditions, this first-order equation determines its subsequent propagation. Its linearity means that the evolution of a quantum superposition is the corresponding quantum superposition of evolved states.

For a real potential energy, this equation and its complex conjugate imply the local continuity equationHere $\rho$ is the probability density and $\mathbf{j}$ the probability current. Vanishing net boundary flux preserves wavefunction normalization, as required by the Born rule.

The time-evolution operator packages the solution for every initial state:Because ${\hat{H}}^{†}=\hat{H}$, differentiation givesTherefore $U^{†}U=I$: this is unitary time evolution, preserving inner products and all state norms. It is reversible, with $U(t,t_0{)}^{-1}=U(t_0,t)=U(t,t_0{)}^{†}$, and obeys the composition law $U(t_2,t_0)=U(t_2,t_1)U(t_1,t_0)$.

For a time-independent Hamiltonian, the solution is the operator exponentialIf the Hamiltonian varies with time, the analogous simple exponential of its integral is valid when $[\hat{H}(t),\hat{H}(t^{\prime })]=0$ for all relevant times. Otherwise time ordering is essential:The meaning is explicit in the first terms of the ordered series,the later-time operator stands on the left. In the position representation, the same propagation is expressed by the quantum-mechanical propagatorIts initial value is the Dirac delta function ${\delta }^3(\mathbf{r}-{\mathbf{r}}^{\prime })$.

A time-independent Hamiltonian has energy eigenstates satisfying $\hat{H}|n⟩=E_n|n⟩$. A single such initial state evolves asIt is a stationary state: its global phase changes, but its probability density and the distributions of time-independent observables do not. Its energy is sharp. Any quantum superposition entirely within one degenerate energy eigenspace also acquires one common global phase and is stationary. Stationarity does not require zero probability current; for instance, $u_n(\varphi )=e^{in\varphi }/\sqrt{2\pi }$ on the ring has a constant density and persistent circulation when $n\ne 0$.

An arbitrary normalized state can instead contain different energy eigenvalues:A continuous spectrum requires corresponding integrals. For the discrete case, an energy measurement gives $E_n$ with fixed probability $|c_n{|}^2$ (summed over degeneracies), but relative quantum phases change with time. ConsequentlyThe interference terms can oscillate at angular frequencies $(E_m-E_n)/\hslash$. For two populated energy levels, this supplies a characteristic period $2\pi \hslash /|E_m-E_n|$ when the interference term is nonzero. Thus fixed energy populations do not imply a stationary spatial distribution.

For a normalized state and an observable $\hat{A}(t)$, its expectation value isThis is the statistical mean over repeated preparations and measurements. In an eigenbasis of energy eigenstates for a time-independent Hamiltonian and a time-independent $\hat{A}$,Only matrix elements connecting different energies can generate these oscillations. If $[\hat{A},\hat{H}]=0$, its expectation value is constant for every initial state, provided it has no explicit time dependence.

Differentiating the expectation value and substituting the Schrödinger equation for both the bra and ket proves the general Ehrenfest theorem:Equivalently,These manipulations require the state to lie in the relevant operator domains. Taking $\hat{A}=\hat{H}$ gives $d⟨H⟩/dt=⟨{\partial }_t\hat{H}⟩$, so energy is conserved under a time-independent Hamiltonian.

For $\hat{H}={\hat{p}}^2/(2m)+V(\hat{x})$, the canonical commutation relation givesHence the particularly useful position-and-momentum form of Ehrenfest theorem isIt resembles Newton's second law, but the mean force generally differs from the force at the mean position. If a narrow wave packet samples a region where the force varies little, $⟨V^{\prime }(x)⟩\simeq V^{\prime }(⟨x⟩)$ gives approximate classical motion. For a quadratic potential energy this replacement is exact. In particular the quantum harmonic oscillator obeysThe centroid follows the classical harmonic oscillator, although this does not specify the full evolving wavefunction or its width.

The Heisenberg picture expresses the same physics by assigning evolution to observables instead:The expectation value is unchanged, and differentiation yields $d{\hat{A}}_H/dt=(i/\hslash )[{\hat{H}}_H,{\hat{A}}_H]+U^{†}({\partial }_t{\hat{A}}_S)U$. Thus state propagation, evolving expectation values, and the classical correspondence in Ehrenfest theorem are mutually consistent descriptions of the same unitary time evolution.

With microstate energies held fixed when differentiating,Since $d\beta /dT=-1/(k_B{T}^2)$,The canonical ensemble fixes volume and particle number, and any other external Hamiltonian parameters. Thus the derivative is $C_V$; pressure-fixed fluctuations would naturally involve enthalpy in a different ensemble.

The translational and two-level energy variance follows because translation and internal states factorize for this dilute classical gas:Differentiating twice yieldsThe terms are independent translational and two-level binomial variances. At $k_{B}T\ll ϵ$, excitation freezes out exponentially and translation dominates. At $k_{B}T\gg ϵ$, the internal variance tends to $N{ϵ}^2/4$ while the translational variance grows as $T^2$; the internal heat capacity consequently tends to zero. Fractional total-energy fluctuations are of order $N^{-1/2}$ for large $N$. The low-temperature statement presumes translation is still nondegenerate; at strictly zero temperature the classical-gas model fails.

First make the units explicit. Use angular momentum operators in units of $\hslash$, so their squared eigenvalues are $J(J+1)$ rather than ${\hslash }^{2}J(J+1)$; the coefficient $A$ then has units of energy. The operator identitygives, at fixed $J_1,J_2$,Subtracting the expression for the adjacent allowed value $J-1$ leavesThis is the Landé interval rule. Its content is that consecutive gaps grow in proportion to the higher total-angular-momentum quantum number, with the same coefficient within an isolated coupled multiplet. A negative $A$ reverses the ordering of the levels, while positive observed transition frequencies alone measure gap magnitudes.

If the source symbols instead denote physical angular momenta with units of action, the Hamiltonian written literally as $A{\mathbf{J}}_1\cdot {\mathbf{J}}_2$ gives the gap $A{\hslash }^{2}J$. Recovering the printed form then requires absorbing ${\hslash }^2$ into the coefficient or writing $H=(A/{\hslash }^2){\mathbf{J}}_1\cdot {\mathbf{J}}_2$. The convention is essential to dimensional consistency rather than an extra dynamical assumption.

Use an orthonormal basis of stationary states and project the Time-dependent Schrödinger equation onto state 2 after removing its free-evolution phase. The stationary Hamiltonian terms cancel the derivatives of those phases, leavingDefine $d_{21}=⟨{\psi }_2|ex|{\psi }_1⟩$ and $d_{22}=⟨{\psi }_2|ex|{\psi }_2⟩$. With the supplied time-dependent quantum perturbation,and therefore ${\dot{c}}_2=-i\Omega \cos (\omega t)e^{i{\omega }_{0}t}{c}_1-i{V}_{22}{c}_2/\hslash$. The state phases may be chosen so $d_{21}$ and $\Omega$ are real for this single driven pair; otherwise probabilities depend on $|\Omega {|}^2$ and the conjugate matrix element appears in the equation for $c_1$. Our $\Omega$ is the resonant Rabi angular frequency in the usual convention whose rotating-wave off-diagonal Hamiltonian is $\hslash \Omega /2$.

For a field-free atom with symmetry under spatial reflection, each selected nondegenerate stationary orbital can be chosen with definite parity. Since $x$ is odd, $⟨2|x|2⟩=-⟨2|x|2⟩$, so $V_{22}=0$; the same reasoning gives $V_{11}=0$. Being an energy eigenstate alone is not sufficient. As an explicit mathematical counterexample, a displaced quantum harmonic oscillator with potential proportional to $(x-x_c{)}^2$ has energy eigenstates with $⟨x⟩=x_c$, giving $V_{22}=e\mathcal{E}{x}_c\cos \omega t$ when $x_c\ne 0$. The vanishing used in the atomic model rests on its parity assumption, not merely on stationarity.

Why degenerate perturbation theory is needed. If several unperturbed states have equal or nearly equal energy, a perturbation can mix them at leading order. In that subspace, diagonalize the perturbation matrix rather than using nondegenerate formulas with small energy denominators. The resulting eigenvectors identify the combinations selected by the coupling, and the eigenvalues give the leading splitting. Other remote states can then be included perturbatively.

For the linear combination of atomic orbitals description of molecular hydrogen, equivalent atomic $1s$ states on the two nuclei supply the nearly degenerate starting functions. In an orthonormal two-state model, equal diagonal energy $E_a$ and real hopping $t$ give $E_a\pm t$ and symmetric/antisymmetric combinations. For actual overlapping atomic functions with overlap $S$ and Hamiltonian coupling $h$, one instead solves a generalized eigenvalue problem:The bonding state has enhanced density between the nuclei and the antibonding state a separating node. Two opposite-spin electrons occupying the bonding molecular orbital describe the simplest closed-shell hydrogen-molecule bond. Electron-electron interaction and nuclear repulsion are needed to calculate a realistic total binding energy; the two-state splitting alone is not the full molecular energy.

In the nearly-free electron model, the analogous degenerate states are plane waves $|\mathbf{k}⟩$ and $|\mathbf{k}-\mathbf{G}⟩$ at a Bragg scattering. A Fourier coefficient $U_{\mathbf{G}}$ of the periodic potential couples them. At exact degeneracy $E_B$, diagonalizing their two-by-two matrix givesThe associated standing waves place electronic density differently relative to the ionic potential. These are the same gap-opening combinations illustrated in Q1(b). The labels of the two starting basis states survive as mixed orbital or plane-wave character, rather than independent crossing eigenstates.

Origin of broad and narrow bands. Spatially extended s/p-derived orbitals have substantial overlap and therefore large hopping amplitudes and broad bands. More localized d orbitals overlap less strongly and produce narrower bands. A multiorbital tight-binding calculation assigns the on-site orbital energies and hopping matrices, forms Bloch sums, and diagonalizes the resulting matrix at each wavevector. Different hopping ranges and orbital symmetry determine the bandwidths and allowed interband coupling. The two-band description retains one broad combination and one nearly flat d-derived combination; a real transition metal contains several d orbitals and more complicated dispersions.

Hybridized eigenvalues and eigenstates. Let $|{\psi }_{\mathbf{k}}⟩=a|{\varphi }_{\mathbf{k}}⟩+b|{\chi }_{\mathbf{k}}⟩$, in an orthonormal basis. Hermitian operator fixes the reverse coupling to be $V^{\ast }$. Projection onto the two components givesSolving this quadratic yields the band hybridization dispersionFor nonzero $V$, one eigenvector representation is $(a,b)\propto (V,E-E_1)$, followed by normalization. Thus the wavefunctions exchange broad-band and d-band character through the avoided crossing; the levels are equal mixtures at the uncoupled crossing.

At $V=0$, the parabola crosses the horizontal level at $k=\pm k_0$, with $k_0=\sqrt{2m{E}_d}/\hslash$. For small nonzero $|V|$, the curves avoid crossing with minimum direct separation $2|V|$. The lower branch follows the parabola below the crossing and flattens toward $E_d$ above it; the upper does the opposite. The lower branch satisfies $E_{-}<E_d$ everywhere and tends to $E_d$ from below as $k\to \infty$, while the upper branch always lies above $E_d$. This is the perfectly flat-band continuum approximation, with zone-boundary intersections excluded as requested.

Fixed particle number and the larger Fermi sphere. Denote the uncoupled broad-band Fermi radius by $k_0$ to distinguish it from the new one $K$. With two spin states, the broad-band number density at $V=0$ is $k_0^3/(3{\pi }^2)$. The stipulated equal population in the flat sector makes the total density twice that value. At zero temperature and any nonzero hybridization, all occupied states fit into the monotonic lower branch below $E_d$, while the upper branch is empty. ThereforeThis is the stated factor increase. It uses fixed total particle number, equal spin counting, an exactly flat unhybridized band and enough available states below any Brillouin-zone restriction. In generic pairs of dispersive bands both hybridized pockets can remain occupied; then Fermi-volume conservation in two hybridized electron bands fixes a sum of volumes rather than this one radius. The exactly flat band is degenerate at $V=0$, so its initial occupation must be specified, as it is here.

Fermi-velocity suppression. Set $\Delta (k)=E_1(k)-E_d$. The exact derivative of the lower branch isAt $k=K$, $E_1(K)=2^{2/3}{E}_d$ and $\Delta (K)=(2^{2/3}-1)E_d>0$. For $|V|\ll \Delta (K)$, the square bracket divided by two is $|V{|}^2/\Delta (K{)}^2+O(|V{|}^4/\Delta (K{)}^4)$. Since group velocity is ${\hslash }^{-1}dE/dk$ and the broad-band reference velocity is $v_F^{(1)}=\hslash k_0/m$,so the flat-band hybridization Fermi-velocity suppression isThe reference velocity is that of the original broad-band Fermi sphere, not the broad-band slope at the larger $K$; omitting the radius change loses the factor $2^{1/3}$.

The low-temperature qualification becomes more stringent as $V\to 0$: the new chemical potential approaches $E_d$ with $E_d-\mu \simeq |V{|}^2/\Delta (K)$, and the relevant thermal energy must be small compared with this hybridization scale. At fixed nonzero temperature the singular flat-band redistribution is not automatically resolved for arbitrarily small coupling. A small but finite narrow-band dispersion can also change the occupation topology.

Density of states and magnetism. For an isotropic three-dimensional branch with spin degeneracy two,A small Fermi velocity therefore produces a large density of states. The localized, partially filled d-derived bands in iron, cobalt and nickel place many states close to the Fermi level; broad s/p-derived conduction bands in copper, silver and gold coexist with filled d bands lying below it. This explains the substantially larger Fermi-level density of states of the former group within the band picture. An exact factor of ten requires the actual band parameters and is not fixed by the two-band toy model.

A high density of states lowers the kinetic-energy cost of spin polarization. A repulsive exchange interaction can then satisfy the Stoner criterion and stabilize ferromagnetism. With a single-spin density of states $g_s$ and an on-site interaction normalization, the criterion is $U{g}_s(E_F)>1$; with spin-summed $g=2g_s$, it is $Ug(E_F)>2$. The large d-state contribution favors this instability in Fe, Co and Ni. The noble metals do not satisfy the corresponding instability condition in the same ordinary state; this does not imply that they have no weak magnetic response whatsoever.

A covalent bond is stabilized by shared electronic states extending across neighboring atomic nuclei. In a simple two-centre description, combining comparable atomic orbitals produces a bonding state with enhanced electron density between the nuclei and an antibonding state with a node there. For equivalent normalized orbitals ${\varphi }_A,{\varphi }_B$ with real overlap $S$,Their energy ordering follows from the molecular Hamiltonian; constructive interference and reduced gradients help explain why the bonding combination can be lower. Opposite-spin electrons can occupy the bonding orbital together. The familiar molecular-hydrogen bond is a basic example, while extended covalent networks form solids such as diamond. Orbital shape and hybridization make covalent bonding strongly directional and constrain bond angles. Occupying antibonding states reduces the net bond strength.

Ionic bonding instead emphasizes electric charge transfer and the electrostatic attraction of the resulting oppositely charged ions. Removing an electron from one atom costs ionization energy and adding it to another gains electron affinity; these isolated-atom terms alone need not favor transfer. In a crystal, the electrostatic lattice energy can stabilize the ionic arrangement. For a schematic lattice of singly charged ions at nearest-neighbor distance $r$,where the geometrical Madelung constant $A_M$ sums attractions and repulsions throughout the lattice. Short-range overlap repulsion prevents collapse and gives an equilibrium separation. Sodium chloride is an example of an extended ionic crystal, rather than isolated NaCl molecules in the solid.

Ideal ionic bonding is comparatively nondirectional, so packing, ion sizes and electric charge balance strongly influence coordination. ions cannot freely migrate in the ordinary solid; melting or dissolution can make ionic electric charge transport possible. Covalent materials do not obey one universal electrical conductivity rule: their electronic bands and filling determine whether mobile electronic carriers are available.

The two descriptions are limiting models, not a sharp classification of every bond. Unequal electronegativities can produce polar covalent bonds with partial electric charge transfer, and a material may contain both covalent groups and ionic interactions between those groups. Chemical bonding reflects a balance of electronic kinetic energy, electron-nucleus attraction, electron-electron repulsion and nuclear repulsion; it cannot be reduced to a force between two assigned point charges in every material.

Both models respect Bloch's theorem and describe electrons in a periodic lattice, but they start from different useful limits.

In the nearly-free electron model, start with extended plane waves and free-electron energies ${\epsilon }_{\mathbf{k}}^0={\hslash }^2{k}^2/(2m)$. A weak periodic potential has Fourier coefficients $V_{\mathbf{G}}$ at reciprocal lattice vectors and couples $\mathbf{k}$ to $\mathbf{k}-\mathbf{G}$. Away from degeneracies its corrections are small. Near a Bragg scattering, retain the two resonant plane waves and diagonalizeThe resulting eigenvalues areAt the crossing the gap is $\boxed{2|V_{\mathbf{G}}|}$. The two standing-wave combinations place electronic density differently relative to the periodic potential and therefore acquire different energies. Folding the many free parabolas into the first Brillouin zone produces the repeated band labels; the nonzero potential opens avoided crossings between coupled states. A Fourier component forbidden by symmetry need not open its corresponding first-order gap.

In the tight-binding model, instead start with localized orbitals on well-separated atoms or sites, with discrete on-site energies. Their overlap permits tunneling represented by hopping integrals. Bloch sums of these orbitals diagonalize the lattice translation symmetry. For one orthonormal orbital per site in a one-dimensional nearest-neighbor chain,The many initially degenerate copies of one atomic orbital broaden into a band. Other atomic orbitals or multiple sites per primitive cell produce additional bands; their hybridization creates bonding and antibonding combinations and may open gaps. For two orbitals per cell, one illustrative Hamiltonian iswith eigenvalues $(E_A+E_B)/2\pm \sqrt{(E_A-E_B{)}^2/4+|t_1+t_2{e}^{-ika}{|}^2}$. This shows explicitly how two bands arise from the two cell degrees of freedom, even when the isolated sites have equal on-site energies.

For each orbital degree of freedom per primitive cell there is one band per spin; band filling and the presence of a gap at the Fermi level determine metallic or insulating behavior. The nearly-free limit emphasizes weak Bragg scattering of extended states, while tight binding emphasizes hopping between localized states. They are complementary approximations to electronic band structure, rather than two incompatible explanations of why periodic solids have bands.

Diagonalization and conventions. The spin-dependent part is $\lambda (-k_y{\sigma }_x+k_x{\sigma }_y)$. For a Hermitian Hamiltonian $\lambda$ is real; the supplied lower-band spinor uses the convention $\lambda >0$, which will be adopted below. The squared spin matrix is ${\lambda }^2(k_x^2+k_y^2)I$. Hence the two ordered energies areIn the $k_z=0$ plane, let $k=\sqrt{k_x^2+k_y^2}$ and $q_R=2m\lambda /{\hslash }^2>0$. ThenIf $\lambda <0$, use $q_R=2m|\lambda |/{\hslash }^2$ to retain the energy ordering, and interchange the spin directions assigned below. This is an isotropic Rashba effect; $q_R$ has units of inverse length, whereas $\lambda$ has units of energy times length.

Band minima. Define $k_R=q_R/2$ and $E_R={\hslash }^2{q}_R^2/(8m)$. Completing the square givesAlong $k_y=k_z=0$, the radial coordinate is $|k_x|$, so the lower branch has two minima:In the full plane these are points on a circle of minima $k=k_R$. Both branches meet at $k=0$, $E=0$. Their ordered energy curves contain $|k_x|$: the lower curve descends from the crossing on either side, while the upper rises. Treating them as globally labeled smooth spin branches without switching labels across $k_x=0$ would obscure the lower-band minima.

Occupied regions and Fermi contours. At zero temperature each spin-split eigenstate with energy below $E_F$ is occupied. PutFor $-E_R<E_F<0$, $0<D<k_R$. The lower-band roots are $k_R-D$ and $k_R+D$, while the upper band is entirely empty. Thus the central disk $k<k_R-D$ is unoccupied, the annulus $k_R-D<k<k_R+D$ is singly occupied, and the exterior is unoccupied. Both Fermi circles belong to the lower band; there is no doubly occupied region.

At $E_F=0$, the lower band is occupied for $0<k<2k_R=q_R$, giving a singly occupied disk with outer Fermi circle at $q_R$. The two bands also meet the Fermi energy at the origin. That isolated degenerate point is not a finite doubly occupied disk, and occupation exactly at the Fermi energy is a boundary convention of zero area. Outside the outer circle the states are empty.