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Rayleigh scattering
Rayleigh scattering
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Rayleigh scattering causes the blue color of the daytime sky and the reddening of the Sun at sunset.

Rayleigh scattering (/ˈrli/ RAY-lee) is the scattering or deflection of light, or other electromagnetic radiation, by particles with a size much smaller than the wavelength of the radiation. For light frequencies well below the resonance frequency of the scattering medium (normal dispersion regime), the amount of scattering is inversely proportional to the fourth power of the wavelength (e.g., a blue color is scattered much more than a red color as light propagates through air). The phenomenon is named after the 19th-century British physicist Lord Rayleigh (John William Strutt).[1]

Due to Rayleigh scattering, red and orange colors are more visible during sunset because the blue and violet light has been scattered out of the direct path. Due to removal of such colors, these colors are scattered by dramatically colored skies and monochromatic rainbows.

Rayleigh scattering results from the electric polarizability of the particles. The oscillating electric field of a light wave acts on the charges within a particle, causing them to move at the same frequency. The particle, therefore, becomes a small radiating dipole whose radiation we see as scattered light. The particles may be individual atoms or molecules; it can occur when light travels through transparent solids and liquids, but is most prominently seen in gases.

Rayleigh scattering of sunlight in Earth's atmosphere causes diffuse sky radiation, which is the reason for the blue color of the daytime and twilight sky, as well as the yellowish to reddish hue of the low Sun. Sunlight is also subject to Raman scattering, which changes the rotational state of the molecules and gives rise to polarization effects.[2]

Scattering by particles with a size comparable to, or larger than, the wavelength of the light is typically treated by the Mie theory, the discrete dipole approximation and other computational techniques. Rayleigh scattering applies to particles that are small with respect to wavelengths of light, and that are optically "soft" (i.e., with a refractive index close to 1). Anomalous diffraction theory applies to optically soft but larger particles.

History

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In 1869, while attempting to determine whether any contaminants remained in the purified air he used for infrared experiments, John Tyndall discovered that bright light scattering off nanoscopic particulates was faintly blue-tinted.[3] He conjectured that a similar scattering of sunlight gave the sky its blue hue, but he could not explain the preference for blue light, nor could atmospheric dust explain the intensity of the sky's color.

In 1871, Lord Rayleigh published two papers on the color and polarization of skylight to quantify Tyndall's effect in water droplets in terms of the tiny particulates' volumes and refractive indices.[4][5][6] In 1881, with the benefit of James Clerk Maxwell's 1865 proof of the electromagnetic nature of light, he showed that his equations followed from electromagnetism.[7] In 1899, he showed that they applied to individual molecules, with terms containing particulate volumes and refractive indices replaced with terms for molecular polarizability.[8]

Small size parameter approximation

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The size of a scattering particle is often parameterized by the ratio

where r is the particle's radius, λ is the wavelength of the light and x is a dimensionless parameter that characterizes the particle's interaction with the incident radiation such that: Objects with x ≫ 1 act as geometric shapes, scattering light according to their projected area. At the intermediate x ≃ 1 of Mie scattering, interference effects develop through phase variations over the object's surface. Rayleigh scattering applies to the case when the scattering particle is very small (x ≪ 1, with a particle size < 1/10 of wavelength[9]) and the whole surface re-radiates with the same phase. Because the particles are randomly positioned, the scattered light arrives at a particular point with a random collection of phases; it is incoherent and the resulting intensity is just the sum of the squares of the amplitudes from each particle and therefore proportional to the inverse fourth power of the wavelength and the sixth power of its size.[10][11] The wavelength dependence is characteristic of dipole scattering[10] and the volume dependence will apply to any scattering mechanism. In detail, the intensity of light scattered by any one of the small spheres of radius r and refractive index n from a beam of unpolarized light of wavelength λ and intensity I0 is given by[12] where R is the observer's distance to the particle and θ is the scattering angle. Averaging this over all angles gives the Rayleigh scattering cross-section of the particles in air:[13] Here n is the refractive index of the spheres that approximate the molecules of the gas; the index of the gas surrounding the spheres is neglected, an approximation that introduces an error of less than 0.05%.[14]

The major constituent of the atmosphere, nitrogen, has Rayleigh cross section of 5.1×10−31 m2 at a wavelength of 532 nm (green light).[14] Over the length of one meter the fraction of light scattered can be approximated from the product of the cross-section and the particle density, that is number of particles per unit volume. For air at atmospheric pressure there are about 2×1025 molecules per cubic meter, and the fraction scattered will be 10−5 for every meter of travel.[citation needed]

The strong wavelength dependence of the scattering (~λ−4) means that shorter (blue) wavelengths are scattered more strongly than longer (red) wavelengths.[citation needed]

From molecules

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Figure showing the greater proportion of blue light scattered by the atmosphere relative to red light

The expression above can also be written in terms of individual molecules by expressing the dependence on refractive index in terms of the molecular polarizability α, proportional to the dipole moment induced by the electric field of the light. In this case, the Rayleigh scattering intensity for a single particle is given in CGS-units by[15] and in SI-units by

Effect of fluctuations

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When the dielectric constant of a certain region of volume is different from the average dielectric constant of the medium , then any incident light will be scattered according to the following equation[16]

where represents the variance of the fluctuation in the dielectric constant .

Cause of the blue color of the sky

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Scattered blue light is polarized. The picture on the right is shot through a polarizing filter: the polarizer transmits light that is linearly polarized in a specific direction.

The blue color of the sky is a consequence of three factors:[17]

  • the blackbody spectrum of sunlight coming into the Earth's atmosphere,
  • Rayleigh scattering of that light off oxygen and nitrogen molecules, and
  • the response of the human visual system.

The strong wavelength dependence of the Rayleigh scattering (~λ−4) means that shorter (blue) wavelengths are scattered more strongly than longer (red) wavelengths. This results in the indirect blue and violet light coming from all regions of the sky. The human eye responds to this wavelength combination as if it were a combination of blue and white light.[17]

Some of the scattering can also be from sulfate particles. For years after large Plinian eruptions, the blue cast of the sky is notably brightened by the persistent sulfate load of the stratospheric gases. Some works of the artist J. M. W. Turner may owe their vivid red colours to the eruption of Mount Tambora in his lifetime.[18]

In locations with little light pollution, the moonlit night sky is also blue, because moonlight is reflected sunlight, with a slightly lower color temperature due to the brownish color of the Moon. The moonlit sky is not perceived as blue, however, because at low light levels human vision comes mainly from rod cells that do not produce any color perception (Purkinje effect).[19]

Of sound in amorphous solids

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Rayleigh scattering is also an important mechanism of wave scattering in amorphous solids such as glass, and is responsible for acoustic wave damping and phonon damping in glasses and granular matter at low or not too high temperatures.[20] This is because in glasses at higher temperatures the Rayleigh-type scattering regime is obscured by the anharmonic damping (typically with a ~λ−2 dependence on wavelength), which becomes increasingly more important as the temperature rises.

In amorphous solids – glasses – optical fibers

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Rayleigh scattering is an important component of the scattering of optical signals in optical fibers. Silica fibers are glasses, disordered materials with microscopic variations of density and refractive index. These give rise to energy losses due to the scattered light, with the following coefficient:[21]

where n is the refraction index, p is the photoelastic coefficient of the glass, k is the Boltzmann constant, and β is the isothermal compressibility. Tf is a fictive temperature, representing the temperature at which the density fluctuations are "frozen" in the material.

In porous materials

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Rayleigh scattering in opalescent glass: it appears blue from the side, but orange light shines through.[22]

Rayleigh-type λ−4 scattering can also be exhibited by porous materials. An example is the strong optical scattering by nanoporous materials.[23] The strong contrast in refractive index between pores and solid parts of sintered alumina results in very strong scattering, with light completely changing direction each five micrometers on average. The λ−4-type scattering is caused by the nanoporous structure (a narrow pore size distribution around ~70 nm) obtained by sintering monodispersive alumina powder.

See also

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Works

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  • Strutt, J.W (1871). "XV. On the light from the sky, its polarization and colour". The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science. 41 (271): 107–120. doi:10.1080/14786447108640452.
  • Strutt, J.W (1871). "XXXVI. On the light from the sky, its polarization and colour". The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science. 41 (273): 274–279. doi:10.1080/14786447108640479.
  • Strutt, J.W (1871). "LVIII. On the scattering of light by small particles". The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science. 41 (275): 447–454. doi:10.1080/14786447108640507.
  • Rayleigh, Lord (1881). "X. On the electromagnetic theory of light". The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science. 12 (73): 81–101. doi:10.1080/14786448108627074.
  • Rayleigh, Lord (1899). "XXXIV. On the transmission of light through an atmosphere containing small particles in suspension, and on the origin of the blue of the sky". The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science. 47 (287): 375–384. doi:10.1080/14786449908621276.

References

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Further reading

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Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Rayleigh scattering is the of , such as visible , by particles that are much smaller than the of the radiation, typically molecules or atoms in a medium like the Earth's atmosphere. This process occurs without a change in the energy of the photons involved, distinguishing it from like . The scattering intensity follows an inverse fourth-power dependence on the (∝ 1/λ⁴), making shorter wavelengths, such as and violet , scatter much more efficiently than longer wavelengths like . This wavelength selectivity is responsible for the color of the daytime , as passing through the atmosphere scatters preferentially in the part of the , with the effect becoming more pronounced away from the direct line of sight to the . The phenomenon was first theoretically described by John William Strutt, 3rd Baron Rayleigh, in his 1871 paper analyzing the polarization and color of skylight. Rayleigh modeled the scattering from small dipole-like particles, deriving the key formula for the scattered intensity and explaining observations of sky polarization. His work built on earlier empirical studies of and laid the foundation for understanding light propagation in gases. Physically, Rayleigh scattering arises when the electric field of an incident electromagnetic wave induces oscillations in the electrons of the scattering particles, which then re-radiate waves in all directions as secondary sources. For particles much smaller than the (typically less than 1/10th), the scattering cross-section is given by σ ∝ (ω/ω₀)⁴ σ_T, where ω is the of the incident , ω₀ is the natural of the particle's electrons, and σ_T is the Thomson cross-section; this results in stronger scattering for higher frequencies. The scattered is also polarized, with the degree of polarization reaching a maximum of 100% at 90° to the incident direction, a property observable in the . Beyond atmospheric effects, Rayleigh scattering plays a critical role in various fields, including attenuation of ultraviolet radiation in the atmosphere, contributing to the reduction of UV flux reaching the surface due to enhanced scattering at short wavelengths. It is also fundamental in optics for analyzing light propagation in transparent media, in for atmospheric profiling, and in for studying molecular interactions. In denser media like liquids or colloids, it contributes to phenomena such as the , though larger particles invoke instead.

Basic Principles

Definition and Conditions

Rayleigh scattering refers to the of electromagnetic waves, such as , or , such as sound, by particles or inhomogeneities whose characteristic dimensions are much smaller than the of the incident , with no net energy transfer to the scatterer. This process was first theoretically described by Lord Rayleigh in his seminal 1871 paper analyzing the polarization and color of . The phenomenon occurs under specific conditions, primarily when the size parameter α=2πaλ1\alpha = \frac{2\pi a}{\lambda} \ll 1, where aa is the radius of the scattering particle and λ\lambda is the of the incident wave. It applies to dilute media, where scatterers are sparsely distributed to avoid multiple events, and to non-absorbing scatterers, ensuring the scattered wave retains the same frequency as the incident wave. These conditions enable the use of the approximation, treating the scatterer as inducing an oscillating that reradiates the wave isotropically except along the incident direction. Rayleigh scattering is distinct from other regimes, such as , which applies to particles comparable to or larger than the and requires solving the full vector wave equations without the small-size simplification. Representative examples include the scattering of visible light by air molecules, which are on the order of angstroms compared to hundreds of nanometers for visible wavelengths, and the scattering of sound waves by atomic-scale defects in solids, where inhomogeneities are much smaller than acoustic wavelengths. A hallmark of Rayleigh scattering is its dependence, with the scattered intensity proportional to λ4\lambda^{-4}, leading to preferential scattering of shorter wavelengths. This inverse fourth-power law arises from the combined effects of the moment's response and the , making it particularly relevant for phenomena involving radiation in the visible or audible spectrum.

Physical Mechanism

Rayleigh scattering arises from the interaction of an incident electromagnetic wave with small scatterers, such as molecules or particles, whose dimensions are much smaller than the of the . The oscillating of the incident wave displaces the electrons within the scatterer, inducing an oscillating that serves as a of radiation. This induced re-radiates electromagnetic waves spherically in all directions, with the scattered propagating away from the scatterer while the original wave continues forward. The magnitude of the induced dipole moment p\mathbf{p} is proportional to the incident electric field E\mathbf{E} through the scatterer's electric polarizability α\alpha, expressed as p=αE\mathbf{p} = \alpha \mathbf{E}. Polarizability α\alpha quantifies the ease with which the scatterer's electron cloud deforms under the applied field, depending on the material's dielectric properties and electronic structure. This classical description captures the essence of the process, where the dipole's oscillation at the frequency of the incident field leads to coherent re-radiation without energy loss to the scatterer./Chapter_8:_Light_Scattering) The scattering is elastic, preserving the frequency (and thus wavelength) of the incident light in the scattered wave, although the direction and phase are randomized relative to the original propagation. The angular distribution of the scattered intensity exhibits a characteristic dipole radiation pattern, proportional to sin2θ\sin^2 \theta, where θ\theta is the scattering angle from the incident direction. Consequently, scattering is minimized in the exact forward (θ=0\theta = 0^\circ) and backward (θ=180\theta = 180^\circ) directions and reaches a maximum at θ=90\theta = 90^\circ for unpolarized incident light. This mechanism extends beyond electromagnetic waves to other wave types, such as , where incident pressure fluctuations in a induce localized variations in small scatterers, analogous to the induced dipoles in light scattering; these perturbations then re-radiate sound waves in all directions. From a quantum mechanical viewpoint, Rayleigh scattering in molecules proceeds via virtual electronic transitions: the incident momentarily excites the system to a virtual intermediate state far from , without real absorption or population of excited states, followed by instantaneous re-emission of a at the original .

Theoretical Formulation

Small Particle Approximation

The small particle approximation in Rayleigh scattering theory arises from solving for the interaction of an electromagnetic with a spherical particle of radius aa much smaller than the λ\lambda, characterized by the size parameter α=2πa/λ1\alpha = 2\pi a / \lambda \ll 1. This regime allows the incident field to be treated as slowly varying across the particle, enabling a perturbative expansion of the exact Mie solution in powers of α\alpha. The approximation was first developed by Lord Rayleigh in his analysis of light scattering by small atmospheric particles. Under the quasi-static approximation, retardation effects within the particle are neglected because the time for light to traverse the particle (a/ca/c) is much shorter than the optical period (λ/c\lambda/c), justifying an electrostatic treatment where the incident field is uniform inside the particle. The problem reduces to solving Laplace's equation 2Φ=0\nabla^2 \Phi = 0 for the scalar potential Φ\Phi both inside and outside the sphere, with the incident field expressed as Einc=Φinc\mathbf{E}_\text{inc} = -\nabla \Phi_\text{inc} and Φinc=Eircosθ\Phi_\text{inc} = -E_i r \cos\theta, where EiE_i is the incident field amplitude and θ\theta is the polar angle. The general solutions are spherical harmonics: inside the sphere (permittivity εs\varepsilon_s), Φin=n=0AnrnPn(cosθ)\Phi_\text{in} = \sum_{n=0}^\infty A_n r^n P_n(\cos\theta); outside (permittivity ε\varepsilon), Φout=Eircosθ+n=0Bnr(n+1)Pn(cosθ)\Phi_\text{out} = -E_i r \cos\theta + \sum_{n=0}^\infty B_n r^{-(n+1)} P_n(\cos\theta). The is solved by enforcing continuity of the tangential (from Φ/θ\partial \Phi / \partial \theta) and the normal displacement field Dr=εΦ/rD_r = \varepsilon \partial \Phi / \partial r at the sphere's surface r=ar = a. For the (n=1n=1) term dominating at lowest order, this yields the scattered potential Φsca=Es(a3/r2)cosθ\Phi_\text{sca} = E_s (a^3 / r^2) \cos\theta, where Es=Ei(εsε)/(εs+2ε)E_s = E_i (\varepsilon_s - \varepsilon)/(\varepsilon_s + 2\varepsilon), corresponding to an induced p=4πεa3Esz^\mathbf{p} = 4\pi \varepsilon a^3 E_s \hat{z}. Higher-order terms (n2n \geq 2) are suppressed by factors of α2n\alpha^{2n}, leading to the full expansion where the Rayleigh approximation retains only the radiation. This model underpins the transition to the more general Mie for larger α\alpha. The approximation holds for α0.3\alpha \lesssim 0.3 in non-absorbing cases with refractive index contrast m10.2|m - 1| \lesssim 0.2 (where m=εs/εm = \sqrt{\varepsilon_s / \varepsilon}
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