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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]

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.

Two atomic orbitals. In the linear combination of atomic orbitals approximation, use $|\psi ⟩=c_A|A⟩+c_B|B⟩$, where the two basis functions are localized atomic orbitals. Projecting $\hat{H}|\psi ⟩=E|\psi ⟩$ onto each orbital gives the generalized eigenvalue problemHere the scalar overlap in the matrix is $S=⟨A|B⟩$, while $H_{ab}=⟨a|\hat{H}|b⟩$. Normalization requires $c^{†}Sc=1$, with $S$ now denoting the full overlap matrix. For equivalent real orbitals with diagonal energy $E_a$, real hopping $t$, and real overlap $s$, the eigenstates and energies areFor the usual negative hopping convention, the symmetric combination is the lower bonding orbital and the antisymmetric combination is the higher antibonding orbital. In an orthonormal approximation, $s=0$ and the result reduces to a two-by-two Hermitian matrix eigenproblem.

Hybridized bands. At each $\mathbf{k}$, take the two Bloch basis states to be orthonormal, as implicit in the stated band model, and write ${ϵ}_k={\hslash }^2{k}^2/(2m)$. The Hamiltonian isFor $|{\psi }_{\mathbf{k}}⟩=a_{\mathbf{k}}|{\varphi }_{\mathbf{k}}⟩+b_{\mathbf{k}}|{\chi }_{\mathbf{k}}⟩$, the eigenvalue condition isso $(E-{ϵ}_k)(E-E_d)-|V{|}^2=0$. Thus band hybridization givesFor nonzero $V$, a convenient explicit normalized pair of eigenstates isA phase convention can make $V$ real, but the eigenvalues depend only on its modulus. These are exact within the truncated two-band model, and approximate as a description of a material.

Dispersions and limits. For $V=0$, the parabola crosses the flat band atFor $V\ne 0$ the crossing is avoided, with a direct hybridization gap $2|V|$ at $k_0$. The lower and upper branches exchange orbital character through this avoided crossing. At the origin their energies areso for $|V|\ll E_d$ the small-$k$ expansions areAt large $k$, where ${ϵ}_k-E_d\gg |V|$,The lower branch approaches $E_d$ from below and becomes flat; the upper branch approaches the free-electron parabola from above. At zero coupling the unsorted orbital bands remain exactly flat and parabolic. Sorting them by energy instead gives $E_{-}=\min ({ϵ}_k,E_d)$ and $E_{+}=\max ({ϵ}_k,E_d)$, which cross at $k_0$ without mixing.

Fermi wavevector and velocity. A partially occupied perfectly flat band has chemical potential $E_d$. Thus before mixing, the occupied broad band has radius $k_0$ defined above. For spin degeneracy two, its particle density is $n_1=k_0^3/(3{\pi }^2)$; equal population of the flat sector gives total density $n=2n_1$.

For any nonzero mixing, $E_{-}(k)<E_d$ at finite $k$, while $E_{+}(k)>E_d$. Moreover $E_{-}(k)$ increases monotonically. At zero temperature and this fixed density, a single occupied sphere in the lower branch therefore accommodates all particles, and the upper branch is empty. Fermi-volume conservation in two hybridized electron bands givesThe new radius is about $26\%$ larger than the old broad-band radius. The strictly flat uncoupled band has no uniquely determined Fermi radius of its own; its prescribed population is what enters the count.

The radial group velocity is $v_{-}(k)={\hslash }^{-1}d{E}_{-}/dk$. Differentiating the exact dispersion givesAt $k_F$, put $\delta =2^{2/3}-1$, so ${ϵ}_{k_F}-E_d=\delta E_d$. Relative to the original broad-band Fermi velocity $v_F^{(1)}=\hslash k_0/m$,Expanding for $|V|\ll E_d$ gives the flat-band hybridization Fermi-velocity suppressionThe coefficient is about $3.65$. The enlarged occupied volume coexists with a small velocity because the new Fermi surface lies on the almost-flat part of the lower branch. This result assumes fixed particle density, sufficient available states before any Brillouin zone boundary, and temperature low enough to resolve energy differences of order $|V{|}^2/E_d$. The limit $V\to 0$ at a fixed nonzero temperature need not give this sharp redistribution. Giving the narrow band a finite dispersion can also leave both pockets occupied, so the result is specific to the ideal model.

Use one orthonormalized localized atomic orbital $|j⟩$ at each position $ja$. In the nearest-neighbour tight-binding model, translation invariance gives the on-site energy and real hopping integralThe Bloch state isSince $H|j⟩=E_0|j⟩+t|j-1⟩+t|j+1⟩$, shifting the two summation indices givesThe hopping integral is an energy, and its sign sets whether $k=0$ is a minimum or maximum. $E_0$ is the diagonal matrix element in the crystal Hamiltonian, which can differ from an isolated-atom energy.

The orthogonal tight-binding approximation matters. If raw neighbouring orbitals retain a nonzero orbital overlap $s$ in their normalization, projection instead gives a generalized eigenvalue problem and the nonorthogonal nearest-neighbour tight-binding band $E(k)=[E_0+2h\cos (ka)]/[1+2s\cos (ka)]$. The stated cosine band follows after orthonormalization and nearest-neighbour truncation, or after neglecting that overlap metric while retaining the hopping it motivates.

Choose one atomic orbital ${\varphi }_A$ and ${\varphi }_B$ on the two atoms and approximate a molecular orbital by the linear combination of atomic orbitalsProjecting the Schrödinger equation onto the two orbitals gives a generalized eigenvalue problem $H\mathbf{c}=ES\mathbf{c}$, where $H_{ij}=⟨{\varphi }_i|\hat{H}|{\varphi }_j⟩$ and $S_{ij}=⟨{\varphi }_i|{\varphi }_j⟩$. In an orthonormal basis the matrix isThe coupling mixes the atomic states and produces a lower bonding molecular orbital and upper antibonding molecular orbital. For equivalent real orbitals with overlap $s$ the normalized combinations are $({\varphi }_A\pm {\varphi }_B)/\sqrt{2(1\pm s)}$; the precise energy ordering follows from the Hamiltonian matrix elements. This restricted orbital basis is an approximation to the molecule's wavefunction, rather than a claim that exact isolated-atom orbitals remain unchanged in the molecule.

A Peierls transition, named for Rudolf Peierls, is a metal-insulator transition caused by a Peierls distortion of an initially metallic chain.^[ref] A modulation at $2k_F$ mixes states near opposite Fermi points and can open a band gap at the Fermi energy. At half filling with one atomic orbital per chemical atom, this modulation doubles the original lattice period and alternates strong and weak bonds. In a weak-coupling zero-temperature description, the Peierls energy gain is proportional to $-({\delta }^2/t)\ln (t/|\delta |)$ whereas the elastic cost is proportional to ${\delta }^2$, where $t>0$ is the undistorted hopping strength and $\delta$ its small alternating change. The logarithm permits a distortion at arbitrarily weak coupling in the ideal model. Finite temperature, finite size, interchain coupling and thermal fluctuations matter for a real transition; strictly one-dimensional reasoning alone does not establish finite-temperature long-range order.

A covalent bond formed through side-on overlap of compatible atomic orbitals, with a nodal plane containing the internuclear axis.

Overlap between adjacent p-type atomic orbitals permits delocalized electronic states across more than one chemical bond. A cyclic path with suitable occupancy can support aromaticity; an external lone pair can act as a donor without contributing an extra independent pair to every ring count.

An atomic orbital with orbital angular momentum quantum number $l=1$. Real $p_x,p_y,p_z$ combinations have opposite quantum phases in their two lobes and a nodal plane through the atomic nucleus. An orbital phase is not an electric charge.

A planar six-membered aromatic ring with nitrogen at opposite ring sites. Its molecular point group is the D2h point group. The six ring $p_z$ atomic orbitals form a six-electron conjugated system; the in-plane nitrogen lone pairs are outside this $\pi$ basis.

A radical has one or more unpaired electrons. In a simple atomic orbital or molecular orbital occupancy picture, an unpaired electron occupies a spatial orbital without an opposite-spin partner in that orbital. A dot such as ${\mathrm{H}}^{\bullet }$ marks this electronic property; it does not mean a missing electron or positive electric charge. Free radicals can be neutral or charged. Terminology also has a boundary: metal ions exhibiting paramagnetism are not normally called free radicals just because they have unpaired electrons.^[ref]

Compare three species containing the same single proton. The hydrogen atom ${\mathrm{H}}^{\bullet }$ has one electron in its $1s$ atomic orbital, and is a neutral radical. The hydrogen cation ${\mathrm{H}}^{+}$ has no electrons, so no unpaired electron. The hydrogen anion ${\mathrm{H}}^{-}$ has two electrons paired in its $1s$ atomic orbital. It is charged but is not a radical in its ground state. With $N_p$ protons, $N_e$ electrons, and positive elementary charge $e$, the independent electric charge count isThe electron pair and electric charge questions require different information. An odd $N_e$ ensures that not all electrons can be paired; an even $N_e$ alone does not ensure pairing, as the molecular orbital description of molecular oxygen illustrates.

The distinction matters whenever a chemical reaction mechanism uses dots and charge signs together. Homolysis gives one bonding electron to each fragment, while heterolysis assigns both to one fragment. A radical chain reaction can pass an unpaired electron from one species to another without generating net electric charge. Detection then exploits the unpaired electron's spin and magnetic moment, rather than merely measuring whether the sample carries an electric charge.

An atomic orbital with orbital angular momentum quantum number zero. Its angular part is spherically symmetric; higher principal shells can have radial nodes.

A spatial orbital is a normalized spatial wavefunction used in a one-particle description. An atomic orbital is the corresponding notion for a chemical atom; a molecular orbital belongs to a molecule. A spatial orbital is not a trajectory and does not by itself specify spin.

A transformation that preserves a specified structure, including the chemical identity of sites in a molecule. Rotations, reflections, inversion and improper rotations can occur in a molecular point group. The associated action on atomic orbitals also changes their orientations and signs, which must be included when computing a character of a representation.

Four equivalent $s$ atomic orbitals at the vertices of a regular tetrahedron carry the tetrahedral symmetry representation $A_1\oplus T_2$. The normalized equal sum is $A_1$; three coordinate-sign combinations span $T_2$. Every normalized coefficient vector has entries $\pm 1/2$ in a suitable orthonormal real basis. These functions simplify a Hamiltonian invariant under the tetrahedral operations, but equivalent symmetry copies on other sites may still mix.

In an orthonormal basis of localized atomic orbitals, a ring of three equivalent sites with real hopping $t$ has Hamiltonian $H=(E_0-t)I+tJ$, where $J$ is the three-by-three all-ones matrix. The normalized symmetric state $(|1⟩+|2⟩+|3⟩)/\sqrt{3}$ has energy $E_0+2t$. Its two-dimensional orthogonal complement has energy $E_0-t$. Thus the symmetric state is the unique spatial ground state for $t<0$, with an energy difference $3|t|$ to the excited eigenstates. Equivalently, the three discrete Bloch states have energies $E_0+2t\cos (2\pi l/3)$, $l=0,\pm 1$. Nonorthogonal atomic orbitals instead require a generalized eigenvalue problem.

An electron occupying an atomic orbital without a partner of opposite spin in that atomic orbital.