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In the Lorentz oscillator model, each participating bound electron is displaced by an applied electric field against a restoring force. The model replaces complicated interband transitions by a driven damped harmonic oscillator. If $u$ is the electron displacement along the field and the electron charge is $-e$, its equation of motion isHere ${\omega }_0$ describes binding and $\gamma >0$ describes loss of coherent motion. For $E(t)=\mathrm{Re}(E_0{e}^{-i\omega t})$, the complex amplitude isThe induced electric dipole moment is $-eu$, so the electric polarization amplitude for number density $n$ isUsing $D={ϵ}_{0}E+P={ϵ}_0{ϵ}_{r}E$ givesThe paper's $ϵ$ is this dimensionless relative permittivity, rather than the absolute permittivity ${ϵ}_0{ϵ}_r$. Independent classes of bound electrons contribute additive susceptibilities, usually with different resonance frequencies and optical oscillator strengths.

Writing $D_{\omega }=({\omega }_0^2-{\omega }^2{)}^2+{\gamma }^2{\omega }^2$ separates the response intoAt zero frequency the real part is $1+{\omega }_p^2/{\omega }_0^2$ and the imaginary part vanishes. Near resonance the imaginary part has a positive photon absorption peak and the real part changes rapidly, passing through $1$ at ${\omega }_0$. Above resonance the real part can become negative when damping is sufficiently weak; at very high frequency it approaches $1$ from below while the imaginary part tends to zero. Finite damping removes the undamped divergence.

For a nonmagnetic material take the passive square-root branch $N=\eta +i\kappa =\sqrt{{ϵ}_r}$, with $\kappa \ge 0$. A plane wave then has an intensity attenuation coefficient $\alpha =2\omega \kappa /c$. Thus the imaginary permittivity expresses dissipation, whereas the actual photon absorption coefficient is determined by the imaginary refractive index. The normal-incidence power reflectance isA large refractive-index mismatch produces wave reflection even without loss. In the undamped model ${ϵ}_r<0$ between ${\omega }_0$ and $\sqrt{{\omega }_0^2+{\omega }_p^2}$, so the field is evanescent and wave reflection is total in a semi-infinite sample. With damping the response includes both wave reflection and photon absorption; a peak in the imaginary permittivity should not simply be identified with a reflectance peak.

To infer the short-wavelength background from $R=0.35$, assume weak photon absorption and take the physical semiconductor branch $\eta >1$. ThensoThis is an estimate of the valence-electron background in a frequency window above the doped-carrier response and below the effective bound-electron resonance. One reflectance value alone does not determine both parts of a complex dielectric constant. Even for real ${ϵ}_r$, a reciprocal-index branch gives the same $R$; the ordinary background index greater than unity selects the branch used here.

Using the supplied conventional cubic lattice parameter, the participating valence-electron number density isUsing $m=m_e$ for the stipulated free-electron comparison givesAn angular frequency “in eV” means its quantum energy $\hslash \omega$, not $h\omega$. No doped-carrier effective mass should be inserted into this valence-electron count.

The low-frequency limit of the bound-electron contribution obeysConsequentlyThis effective resonance is much larger than the quoted $0.2\mathrm{eV}$ band gap. There is no contradiction: the single oscillator has been assigned the strength of all sixteen participating valence electrons per conventional cell, whereas the band gap is only the lowest interband excitation threshold. A real spectrum distributes optical oscillator strength over many transitions. Equating the oscillator resonance to the lowest threshold would misrepresent the assumed background response. Here “low frequency” means low relative to ${\omega }_0$; the static response of the doped conducting sample also contains its free carriers.

The additional mobile carriers in doped indium antimonide contribute a Drude frequency response, obtained by setting their restoring frequency to zero. At infrared frequencies well below the effective valence resonance, the sum is approximatelyAt the shorter wavelengths the carrier term is small and $R$ approaches the background value. As wavelength increases, the negative free-carrier contribution lowers the real permittivity towards unity. For weak damping, refractive-index matching to vacuum gives the Drude-Lorentz reflectivity minimum atThis minimum is near ${ϵ}_r^{\prime }=1$, not its zero. At the slightly lower screened plasma frequency ${\omega }_{pc}/\sqrt{{ϵ}_b}$, the real permittivity crosses zero; at longer wavelengths it becomes negative and the material becomes strongly reflective. Finite damping prevents a perfectly vanishing minimum and rounds the edge. At still lower frequency the large conducting response also drives $R$ towards unity.

For fixed carrier effective mass and background permittivity, ${\omega }_{pc}\propto \sqrt{n_c}$ and ${\lambda }_{\min }\propto n_c^{-1/2}$. The observed shift of the minimum towards shorter wavelength as doping increases is therefore the expected free-carrier trend. The figure is an original model illustration, not a digitization or quantitative fit of the supplied curves; the carrier effective mass, damping and their density dependence have not been specified.

Choose the $e^{-i\omega t}$ convention. The steady displacement in the Lorentz oscillator model has complex amplitudeThe induced electric dipole moment is $p_{\omega }=q{u}_{\omega }$, so the microscopic electric polarizability is $\alpha (\omega )=q^2/[m({\omega }_T^2-{\omega }^2-i\gamma \omega )]$. For $N$ identical oscillators per unit volume, $P_{\omega }=N{p}_{\omega }={ϵ}_0{\chi }_{\omega }{E}_{\omega }$. ConsequentlyHere the dimensionless quantity called polarizability in the paper is the electric susceptibility; the single-electron polarizability $\alpha$ has different units. The sign of the electron charge disappears because both the driving force and dipole moment contain $q$.

Multiplying by the complex conjugate of the denominator givesFor positive damping and positive frequency, ${ϵ}_r^{\prime \prime }\ge 0$, as required for passive wave absorption in this Fourier convention. At zero frequency, ${ϵ}_r^{\prime }=1+{\omega }_p^2/{\omega }_T^2$ and ${ϵ}_r^{\prime \prime }=0$. Near a weakly damped resonance the imaginary part has a narrow positive peak, while the real part rises on the low-frequency side and then falls steeply through ${ϵ}_r^{\prime }=1$ at ${\omega }_T$. It can become negative above resonance for sufficiently strong oscillator strength and weak damping. At large frequency, ${ϵ}_r^{\prime }=1-{\omega }_p^2/{\omega }^2+O({\omega }^{-4})$ and ${ϵ}_r^{\prime \prime }\sim {\omega }_p^2\gamma /{\omega }^3$: both approach the vacuum values. The absorption maximum is close to, but need not be exactly at, ${\omega }_T$ for finite damping.

A primitive cell containing two atoms has two independent displacement coordinates for each chosen polarization. Their coupled normal modes split into an acoustic phonon branch, which translates the cell at long wavelength, and an optical phonon branch, which moves its constituents against one another. The nonzero restoring force for the relative displacement gives a nonzero optical frequency even at the zone centre.

For an explicit scalar model, take alternating masses $M,m$, equal nearest-neighbor spring constant $K$, and cell length $a$. If $u_n,v_n$ are the displacements of the two atoms in cell $n$, Newton's second law givesA mode proportional to $e^{i(kna-\omega t)}$ has a nonzero amplitude only when the two-by-two dynamical determinant vanishes. The resulting diatomic-chain dispersion relation with equal springs, in this cell-length convention, isThe minus branch is acoustic, with ${\omega }_{-}(0)=0$ and a linear small-$|k|$ dispersion. The plus branch is optical, withAt $k=0$, the acoustic eigenvector has $u=v$. The optical eigenvector instead satisfies $Mu+mv=0$: its cell centre of mass stays fixed while the atoms move oppositely. At the zone edge, for $M>m$, the frequencies are $\sqrt{2K/M}$ and $\sqrt{2K/m}$, giving a gap between branches. Both slopes vanish there. The dispersion and displacement patterns are shown in the preceding original figure.

If the two atoms carry opposite effective charges, the relative motion creates an oscillating electric dipole moment, enabling infrared absorption by long-wavelength light. The photon momentum is tiny compared with the zone size, so ordinary optical absorption principally excites modes close to $k=0$. Raman activity instead depends on modulation of polarizability; the name optical does not imply that every such mode is infrared active. Three-dimensional crystals have separate longitudinal and transverse polarizations, and long-range Coulomb forces can split their optical frequencies. A monatomic primitive cell has no internal relative coordinate and therefore no optical branch of this type.

For independent electronic transitions, add the electric dipole moment responses:The positive constants $S_j$ include electron density and transition atomic oscillator strength. Each term adds an absorption peak to ${ϵ}_r^{\prime \prime }$ and a dispersive positive-to-negative contribution to ${ϵ}_r^{\prime }-1$, as in the middle row of the figure.

Between well-separated absorption lines, where the medium is transparent, the refractive index generally increases with frequency: $d{n}_r/d\omega >0$, or $d{n}_r/d\lambda <0$. This is normal dispersion. Near a resonance the real response turns down with increasing frequency, producing an interval of anomalous dispersion, $d{n}_r/d\omega <0$, accompanied by appreciable absorption. The absorptive and dispersive parts are linked by the Kramers-Kronig relations; the steep variation is not independent of the loss spectrum.

Choose $A^{\mu }=(\Phi ,\mathbf{A})$, so that $F_{i0}=E_i$ and $F_{ij}={ϵ}_{ijk}{B}_k$, with ${ϵ}_{123}=1$. The definitions of the polarization-magnetization tensor imply $M^{0i}=-P_i$ and $M^{ij}={ϵ}_{ijk}{M}_k$. Separating temporal and spatial indices,The Levi-Civita symbol contraction equals $2{\delta }_{k\ell }$, givingThus $\mathbf{P}$ is the electric dipole moment per volume, or electric polarization, and $\mathbf{M}$ is the magnetic dipole moment per volume, or magnetization. The signs are those of dipole interactions in a Lagrangian; the associated fixed-dipole potential energies have the opposite signs. Consistently, the equation in part (a) has componentsso ${\rho }_b=-\nabla \cdot \mathbf{P}$ and ${\mathbf{J}}_b={\partial }_t\mathbf{P}+\nabla \times \mathbf{M}$ are the bound charge and bound current.

An electrically small perfect conductor sphere has both an induced electric dipole moment and magnetic dipole moment. The latter contributes half the electric scattering amplitude in magnitude. The two amplitudes add in the backward direction and partially cancel in the forward direction. Thus the backward intensity is $9/4$ of the electric-only value and its radar cross section is $9\pi k^4{a}^6$. The correction persists at leading order as $ka\to 0$; discarding the magnetic term is a separate response approximation.^[ref]

Permittivity describes how an electric field and a material's electric polarization combine into the electric displacement field. In a static, local response with linearity and isotropy, and no electric polarization at zero electric field, the constitutive equation isHere ${ϵ}_0$ is vacuum permittivity, while ${ϵ}_r$ is the relative permittivity, a dimensionless quantity. The SI unit of permittivity is farad per metre, $F/m$: multiplying it by an electric field in $V/m$ gives an electric displacement field in $C/{\mathrm{m}}^2$. A larger positive permittivity lets the same parallel-plate capacitor hold more plate electric charge at the same electric potential difference.

The material contribution is electric polarization $\mathbf{P}$, the electric dipole moment per unit volume. The electric displacement field and electric susceptibility ${\chi }_e$ satisfySubstitution gives the first constitutive equation. The electric field here is the averaged, total field inside the material, not just the field of the external plate electric charges. The continuum approximation averages over many chemical atoms or molecules; locality means that the electric polarization at a position depends on the electric field there. Static equilibrium, fixed material conditions and sufficiently small electric fields are needed for this scalar proportionality. ^[ref].

For an ideal parallel-plate capacitor completely filled by a uniform dielectric, hold the free plate electric charge magnitude $Q$ fixed and neglect the fringing field of a capacitor. Writing $A$ for the plate area, Gauss's law gives $D=Q/A$. ThusThe electric dipoles point along the electric field. Their surface electric charges, described by polarization density, oppose the field from the free plate electric charges. For a hypothetical dielectric with ${ϵ}_r=4$, the internal electric field is one quarter of its vacuum value, while $P=3D/4$. At fixed electric potential difference instead, the internal electric field stays approximately $V/d$ and the plate electric charge grows fourfold. These are different experimental constraints. ^[ref].

Permittivity is a useful material summary, not a universal constant of the material under every condition. Temperature, frequency and electric field strength can change the response. In a linear anisotropic dielectric, permittivity is a tensor, $D_i={\sum }_j{ϵ}_{ij}{E}_j$, so the electric displacement field need not be parallel to the electric field. At nonzero frequency, delayed electric polarization requires complex permittivity and may produce dielectric loss. ^[ref].

For $\ddot{z}+2\gamma \dot{z}+{\omega }_0^{2}z=(q{E}_0/m)\cos \omega t$, the $e^{i\omega t}$ convention gives complex displacement amplitude $\tilde{z}=(q{E}_0/m)/({\omega }_0^2-{\omega }^2+2i\gamma \omega )$. If the real amplitude is defined nonnegative, the phase is $-\delta$ for $q>0$ but $\pi -\delta$ for $q<0$, where $\delta =atan2(2\gamma \omega ,{\omega }_0^2-{\omega }^2)$. An electron's low-frequency displacement is opposite to the electric field; its high-frequency displacement is in phase. The induced electric dipole moment $qz$ instead has phase $-\delta$ for either sign of charge. A signed amplitude can absorb the extra $\pi$, but that convention must be stated.

A polar covalent bond shares electrons unequally, as in hydrogen chloride.

The word “polar” qualifies the sharing within a covalent bond; it does not require complete transfer of an electron or an isolated cation–anion pair. In $A^{\delta +}-B^{\delta -}$, the signs identify the relatively electron-poor and electron-rich ends, while $\delta$ leaves the amount unspecified. A neutral Lewis structure can give both chemical atoms zero formal charge and still correspond to a polar covalent bond: equal division of the bond pair is a formal allocation, whereas bond polarization concerns the actual electron density.

Local and molecular descriptions answer different questions. Calling one chemical bond a polar covalent bond does not establish that the whole molecule is a polar molecule. Combine the bond dipoles with the molecular geometry, then check for molecular dipole cancellation. This lets a short electronegativity comparison explain a local tendency without confusing it with the observable electric dipole moment of the whole molecule.

The linear response relating an induced electric dipole moment to an applied electric field. In ordinary nonresonant Raman spectroscopy, changes in its symmetric components during a normal mode determine activity. These components transform like $x^2,y^2,z^2,xy,xz,yz$.

Viewed perpendicular to the magnetic field, the normal Zeeman effect has a $\pi$ component with linear polarization parallel to the magnetic field and two $\sigma$ components polarized perpendicular to it. Along the magnetic field, $\pi$ vanishes and the $\sigma$ pair has opposite circular polarizations. Pieter Zeeman described these geometry-dependent patterns in his lecture.^[ref]

The geometry can be derived from electric dipole radiation. Let the observation unit vector be $\mathbf{n}=(\sin \theta ,0,\cos \theta )$, with $\theta$ measured from the magnetic field. Radiation retains only the transverse part of the oscillating electric dipole moment $\mathbf{d}$:For $\pi$, take $\mathbf{d}\parallel \hat{\mathbf{z}}$; its angular light intensity factor is ${\sin }^2\theta$, so it vanishes on axis. For ${\sigma }^{\pm }$, use normalized complex dipoles $(\hat{\mathbf{x}}\pm i\hat{\mathbf{y}})/\sqrt{2}$. Their angular factors are $(1+{\cos }^2\theta )/2$. Projection gives circles on axis, lines at $\theta =\pi /2$, and generally elliptical polarization between. These factors assume equal dipole magnitudes; actual line light intensities also depend on initial quantum state populations, transition strengths and collection geometry. No absolute handedness name is needed: it depends on the viewing and phase conventions.

A transverse polarizer can separate $\pi$ from $\sigma$ even before the spectral line components are fully resolved. Along the magnetic field, a quarter-wave plate followed by a polarizer converts the two opposite circular polarizations into distinguishable linear settings. This explains why polarization analysis carried information beyond a small increase in line width.

A polar molecule has a nonzero permanent electric dipole moment because of its internal electric charge distribution. It can still have zero total electric charge. Water is polar; a nonpolar molecule has no permanent electric dipole moment.

For the field-free, spin-free linear rigid rotor in one fixed internal quantum state, the electric-dipole interaction is $-\mathbf{d}\cdot \mathbf{E}(t)$. A nonzero permanent electric dipole moment along the molecular axis allows pure rotational photon absorption with $\Delta J=+1$ and photon emission with $\Delta J=-1$. The matrix element between initial and final quantum states must be nonzero: the existence of an energy gap alone is insufficient. Relative to a chosen $z$ axis, polarization of an electromagnetic wave along $z$ selects $\Delta M=0$; transverse polarization of an electromagnetic wave permits $\Delta M=\pm 1$.^[ref]

Hydrogen chloride and carbon monoxide are examples with a permanent electric dipole moment. By symmetry, molecular hydrogen and carbon dioxide have no permanent electric dipole moment in the ideal symmetric internal state. They still rotate and have rotational energy eigenvalues, but the simple permanent-electric dipole spectrum described here is absent. This restriction concerns this interaction and these assumptions, not every possible way of detecting molecular rotation.

A permanent electric dipole moment of magnitude $p_0$ rotating perpendicular to a fixed axis emits $P=K{\omega }^4$ in the electric-dipole approximation for radiation, with $K={\mu }_0{p}_0^2/(6\pi c)$. For fixed mechanical moment of inertia $\mathcal{I}$, weak radiative loss gives $\mathcal{I}\omega \dot{\omega }=-K{\omega }^4$ and hence the displayed spin-down law. It assumes $|\dot{\omega }|\ll {\omega }^2$: the full dipole acceleration has squared magnitude $p_0^2({\omega }^4+{\dot{\omega }}^2)$, whose second term is beyond this leading adiabatic approximation.

The simplest off-resonant explanation is a vibrating polarizability. Let $Q(t)=Q_0\cos (2\pi {\nu }_{v}t)$ be a small normal mode coordinate of molecular vibration, and use one scalar component of polarizability, $\alpha (Q)\simeq {\alpha }_0+{\alpha }_0^{\prime }Q$. For incident electric field $E(t)=E_0\cos (2\pi {\nu }_{0}t)$, the induced electric dipole moment isThe product-to-sum formula produces the two displaced frequencies. A nonzero derivative ${\alpha }_0^{\prime }$ gives vibrational Raman scattering in this linear model. Real polarizability is generally a tensor, and the selected components depend on incident and observed wave polarization. This condition differs from vibrational infrared activity, which requires a changing molecular electric dipole moment without an applied optical electric field. A vibration can therefore appear in one measurement and be absent in the other.

This classical modulation argument explains line locations but supplies equal sideband wave amplitudes; it does not explain their thermal asymmetry or the nonzero Stokes Raman scattering from a vibrational ground state. Those require the quantum harmonic oscillator population and transition strengths. The far-off-resonance drawing uses dashed virtual intermediate levels: they represent terms in a scattering probability amplitude, not a long-lived occupied electronic energy eigenstate. Near an electronic resonance, a more detailed treatment of the intermediate response is needed.

Rayleigh scattering is elastic scattering of electromagnetic radiation by particles much smaller than the incident wavelength. In the stationary particle approximation, the scattered electromagnetic radiation keeps the incident frequency: its direction changes, rather than its color. The incident electric field induces an oscillating electric dipole moment, which produces electric dipole radiation. This is a useful example of how a microscopic response can explain a familiar large-scale sight, why the sky is blue. ^[ref].

The smallness condition for Rayleigh scattering by a small sphere of radius $a$ is $ka\ll 1$, where the wavenumber is $k=2\pi /\lambda$ and $\lambda$ is the surrounding medium's wavelength. For ordinary materials with modest refractive index, the incident electric field then varies little across the particle, making the electric-dipole approximation for radiation useful. For very large refractive index, also check the internal size $|m|ka\ll 1$ before applying the simple electric dipole model. Once these conditions fail, use Mie scattering for a sphere instead of extrapolating the Rayleigh scattering wavelength dependence.

Historically, the 1871 paper ^[ref] connected the color and polarization of an electromagnetic wave of scattered skylight with particles smaller than the wavelength. Its dimensional analysis anticipates scattered light intensity proportional to particle volume squared and to ${\lambda }^{-4}$. The original mechanical picture is historical; the modern explanation uses induced electric dipole radiation.

For incident unpolarized light and the isotropic electric dipole response of Rayleigh scattering by a small sphere, let $\theta$ be the angle between the incident beam's propagation direction and the outgoing direction. The differential scattering cross-section and its relative angular pattern arewhere $d\Omega$ is an element of solid angle. Averaging over the two transverse directions of incident polarization of an electromagnetic wave gives this pattern. Forward scattering at $0^{\circ }$ and backward scattering at $180^{\circ }$ are equally strong: $F=1$. Sideways scattering at $90^{\circ }$ is weakest, but nonzero: $F=1/2$. ^[ref].

The normalization is consistent becauseThus integrating $d\sigma /d\Omega$ gives the total Rayleigh scattering cross-section $\sigma$. The plotted $F$ has maximum one; it is not itself normalized to unit solid angle integral.

For a single electric dipole driven by incident linear polarization, the angular distribution of electric dipole radiation instead has a ${\sin }^2\alpha$ factor, where $\alpha$ is measured from the electric dipole moment direction, parallel to the incident electric field. That direction is perpendicular to the incident beam. Confusing $\alpha$ with the beam angle $\theta$ would incorrectly predict zero forward scattering. Averaging the dipole patterns over incident unpolarized light yields the displayed $F(\theta )$.

Consider a fixed, homogeneous, nonabsorbing, nonmagnetic sphere of radius $a$ in vacuum. Let $m$ be its relative refractive index, a fixed real number; in vacuum this equals the sphere's refractive index. Treat $m$ as independent of wavelength over the range being compared, neglecting optical dispersion. Air can be approximated by vacuum here because its refractive index is close to one. These assumptions describe a toy particle, rather than a literal model of an individual air molecule.

The Rayleigh scattering cross-section $\sigma$ is an effective area: the total scattered power is $P_{\mathrm{sca}}=I_{\mathrm{inc}}\sigma$, where $I_{\mathrm{inc}}$ is the incident light intensity. For $ka\ll 1$ its leading approximation isThe units are area, since $k^4{a}^6$ has units ${\mathrm{m}}^{-4}{\mathrm{m}}^6={\mathrm{m}}^2$. This Rayleigh scattering cross-section measures scattering, not conversion of the incident electromagnetic radiation into heat. The definition follows ^[ref].

To see the mechanism, the nearly uniform applied electric field produces an electric dipole moment with peak magnitudewhere $E_0$ is the incident electric field peak wave amplitude and ${ϵ}_0$ is vacuum permittivity. This is the sphere's response in electrostatics, with its permittivity divided by vacuum permittivity equal to $m^2$ under the nonmagnetic assumption. ^[ref]. The averaged electric dipole radiation power is $P_{\mathrm{sca}}={\omega }^4{p}_0^2/(12\pi {ϵ}_0{c}^3)$, with angular frequency $\omega =ck$ and speed of light $c$. Dividing by $I_{\mathrm{inc}}={ϵ}_{0}c{E}_0^2/2$ gives the displayed Rayleigh scattering cross-section. Thus doubling radius multiplies the electric dipole moment by eight and the scattered power by $64$, provided the larger sphere still satisfies $ka\ll 1$. ^[ref].

An ideal electric dipole at the origin with smooth electric dipole moment $\mathbf{p}(t)$ has Lorenz gauge electric potential and magnetic vector potential, for $r>0$,For a short proof, place electric charges $sq$ at $s\mathbf{p}/(2q)$, $s=\pm 1$, and let $q\to \infty$ with $\mathbf{p}$ fixed. The corresponding retarded times are $t_0+s\mathbf{n}\cdot \mathbf{p}(t_0)/(2qc)+O(q^{-2})$. Each Liénard–Wiechert potential has denominator $r-s(\mathbf{n}\cdot \mathbf{p}+r\mathbf{n}\cdot {\mathbf{p}}^{\prime }/c)/(2q)+O(q^{-2})$. The opposite $q/r$ terms cancel, leaving the displayed electric potential. The products of signed electric charge and velocity add, giving the displayed magnetic vector potential. Bounded time derivatives on the relevant interval justify the Taylor expansions.

Rotational Raman spectroscopy observes a frequency change of scattered light associated with molecular rotation. The coupling uses the induced electric dipole moment, ${\mathbf{d}}_{\mathrm{ind}}=\mathbf{\alpha }\mathbf{E}$, where $\mathbf{\alpha }$ is the electric polarizability tensor. For a linear molecule, the useful anisotropy is ${\alpha }_{\parallel }-{\alpha }_{\perp }$: the response differs for an electric field parallel or perpendicular to the molecular axis. A permanent electric dipole moment is not required.^[ref]

For the spin-free linear rigid rotor in one internal quantum state, the anisotropic tensor depends quadratically on the molecular direction. Its angular part has even parity and degree two in spherical harmonics. The triangle inequality for coupled angular momenta permits $|\Delta J|\le 2$, and even parity removes odd $\Delta J$, leaving $\Delta J=0,\pm 2$. The $\Delta J=0$ contribution is unshifted light; shifted rotational lines have $\Delta J=\pm 2$. Consequently the rigid-model Stokes shifts, in ordinary frequency units, areSuccessive allowed shifts are separated by $4B$, rather than the $2B$ absorption spacing of pure rotational electric-dipole selection rules. In spectroscopic wavenumber units replace $B$ by $\tilde{B}=B/c$ and $\Delta \nu$ by $\Delta \tilde{\nu }=\Delta \nu /c$, using the speed of light in $\mathrm{cm}{\mathrm{s}}^{-1}$ for $\mathrm{c}{\mathrm{m}}^{-1}$.

A homonuclear diatomic molecule such as molecular hydrogen has no permanent electric dipole moment in its symmetric internal state, so it lacks the ordinary electric-dipole microwave ladder. Its anisotropic electric polarizability can nevertheless give rotational Raman spectroscopy lines. Nuclear-spin symmetry can change the populations of even and odd $J$ levels, so the spin-free population example above must not be reused unchanged for molecular hydrogen. The method of coupling, as well as the energy eigenvalues, determines what the experiment can see.