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diff --git a/source/know/concept/clausius-mossotti-relation/index.md b/source/know/concept/clausius-mossotti-relation/index.md new file mode 100644 index 0000000..a0f4916 --- /dev/null +++ b/source/know/concept/clausius-mossotti-relation/index.md @@ -0,0 +1,264 @@ +--- +title: "Clausius-Mossotti relation" +sort_title: "Clausius-Mossotti relation" +date: 2024-04-14 +categories: +- Physics +- Electromagnetism +layout: "concept" +--- + +The **polarizability** $$\alpha$$ of a small dielectric body (e.g. an atom or molecule) +is defined to relate the [electric field](/know/concept/electric-field/) $$\vb{E}$$ +applied to that body to the resulting dipole moment $$\vb{p}$$: + +$$\begin{aligned} + \vb{p} + = \alpha \varepsilon_0 \vb{E} +\end{aligned}$$ + +If there are $$N$$ such bodies per unit volume, +the polarization density $$\vb{P} = \varepsilon_0 \chi_e \vb{E}$$ +with $$\vb{P} = N \vb{p}$$ suggests that $$\chi_e = N \alpha$$. +However, this is an underestimation: +each body's induced dipole creates its own electric field, +weakening the field felt by its neighbors. +We need to include this somehow, +but $$\alpha$$ is defined for a single dipole in a vacuum. + +Let $$\vb{E}_\mathrm{int}$$ be the uniform internal field excluding the dipoles' contributions, +and $$\vb{E}(\vb{r})$$ the net field including them. +Assume that the dipoles $$\vb{p}_i$$ are arranged +in a regular crystal lattice at sites $$\vb{R}_i$$. +Then $$\vb{E}(\vb{r})$$ is the sum of $$\vb{E}_\mathrm{int}$$ and all the dipoles' fields: + +$$\begin{aligned} + \vb{E}(\vb{r}) + = \vb{E}_\mathrm{int} + \sum_{i} \vb{E}_i(\vb{r} - \vb{R}_i) +\end{aligned}$$ + +Where the individual contribution $$\vb{E}_i(\vb{r})$$ +of each dipole $$\vb{p}_i$$ is as follows: + +$$\begin{aligned} + \vb{E}_i(\vb{r}) + = - \frac{1}{4 \pi \varepsilon_0} \nabla \bigg( \frac{\vu{r} \cdot \vb{p}_i}{|\vb{r}|^2} \bigg) +\end{aligned}$$ + +{% include proof/start.html id="proof-dipole" -%} +The atoms or molecules $$\vb{p}_i$$ need not be perfect dipoles, +as long as they approximate one when viewed from a distance +much smaller than the crystal's lattice constant. +Clearly, in a multipole expansion +of the true charge distribution $$\rho_i(\vb{r})$$'s electric potential $$V_i(\vb{r})$$, +the dipole term will be dominant in that case, given by: + +$$\begin{aligned} + V_i(\vb{r}) + \approx \frac{1}{4 \pi \varepsilon_0} \frac{1}{|\vb{r}|^2} \int \rho_i(\vb{r}') \: |\vb{r}'| \cos{\theta} \dd{\vb{r}'} +\end{aligned}$$ + +Where $$\theta$$ is the angle between $$\vb{r}$$ and $$\vb{r}'$$, +so this can be rewritten as a dot product +with the unit vector $$\vu{r}$$, normalized from $$\vb{r}$$: + +$$\begin{aligned} + V_i(\vb{r}) + = \frac{1}{4 \pi \varepsilon_0} \frac{1}{|\vb{r}|^2} \: \vu{r} \cdot \!\!\int \vb{r}' \rho_i(\vb{r}') \dd{\vb{r}'} +\end{aligned}$$ + +The integral is a more general definition of the dipole moment $$\vb{p}_i$$. +You can convince yourself of this by defining $$\rho_i(\vb{r})$$ +as two opposite charges $$+q$$ and $$-q$$ +respectively located at $$+\vb{d}_i/2$$ and $$-\vb{d}_i/2$$; +evaluating the integral then yields $$q \vb{d}_i = \vb{p}_i$$. +Therefore: + +$$\begin{aligned} + V_i(\vb{r}) + = \frac{1}{4 \pi \varepsilon_0} \frac{\vu{r} \cdot \vb{p}_i}{|\vb{r}|^2} +\end{aligned}$$ + +Then the corresponding electric field $$\vb{E}_i$$ is given by $$- \nabla V_i$$ as is well known. +{% include proof/end.html id="proof-dipole" -%} + +The dipole $$\vb{p}_0$$ at $$\vb{r} = 0$$ +feels a net local field $$\vb{E}_\mathrm{loc}$$, given below. +The crystal's symmetry ensures that all its neighbors' fields cancel out: +since $$\vb{E}_i(-\vb{r}) = -\vb{E}_i(\vb{r})$$, +each dipole has a counterpart with the exact opposite field. +We exclude the singular term $$\vb{E}_0(0)$$: + +$$\begin{aligned} + \vb{E}_\mathrm{loc} + \equiv \vb{E}(0) + = \vb{E}_\mathrm{int} + \sum_{i \neq 0} \vb{E}_i(-\vb{R}_i) + = \vb{E}_\mathrm{int} +\end{aligned}$$ + +Even if there is no regular lattice, this result still holds well enough, +as long as the dipoles are uniformly distributed over a large volume. + +So what was the point of including $$\vb{E}_i(\vb{r})$$ in the first place? +Well, keep in mind that the sum over neighbors is nonzero for $$\vb{r} \neq \vb{R}_i$$, +which *does* affect the macroscopic field $$\vb{E}$$, defined as: + +$$\begin{aligned} + \vb{E} + = \vb{E}_\mathrm{loc} + + \frac{1}{\Omega} \int_\Omega \sum_i \vb{E}_i(\vb{r} - \vb{R}_i) \dd{\vb{r}} +\end{aligned}$$ + +Where $$\Omega$$ is an arbitrary averaging volume, +large enough to contain many dipoles, +and also small enough to assume that the polarization is uniform within. +Thanks to linearity and symmetry, +we only need to evaluate this volume integral for a single dipole: + +$$\begin{aligned} + \int_\Omega \vb{E}_i(\vb{r}) \dd{\vb{r}} + &= - \frac{1}{4 \pi \varepsilon_0} \int_\Omega \nabla \bigg( \frac{\vu{r} \cdot \vb{p}_i}{|\vb{r}|^2} \bigg) \dd{\vb{r}} + \\ + &= - \frac{1}{4 \pi \varepsilon_0} \oint_{\partial \Omega} \frac{\vu{r} \cdot \vb{p}_i}{|\vb{r}|^2} \dd{\vu{n}} +\end{aligned}$$ + +Where we have used the divergence theorem. +Let us define $$\Omega$$ as a sphere with radius $$R$$ centered at $$\vb{r} = 0$$. +In [spherical coordinates](/know/concept/spherical-coordinates/), +the surface integral then becomes: + +$$\begin{aligned} + \int_\Omega \vb{E}_i(\vb{r}) \dd{\vb{r}} + &= - \frac{1}{4 \pi \varepsilon_0} \int_0^\pi \int_0^{2 \pi} + \frac{\vu{r} \cdot \vb{p}_i}{|\vb{r}|^2} \: \vu{r} \: |\vb{r}|^2 \sin{\theta} \dd{\varphi} \dd{\theta} +\end{aligned}$$ + +The radial coordinate disappears, so in fact the radius $$R$$ is irrelevant. +We choose our coordinate system such that $$\vb{p}_i$$ points +in the positive $$z$$-direction, i.e. $$\vb{p}_i = (0, 0, |\vb{p}_i|)$$, leaving: + +$$\begin{aligned} + \int_\Omega \vb{E}_i(\vb{r}) \dd{\vb{r}} + &= - \frac{|\vb{p}_i|}{4 \pi \varepsilon_0} \int_0^\pi \int_0^{2 \pi} + \begin{pmatrix} + \sin{\theta} \cos{\varphi} \\ + \sin{\theta} \sin{\varphi} \\ + \cos{\theta} + \end{pmatrix} + \sin{\theta} \cos{\theta} \dd{\varphi} \dd{\theta} +\end{aligned}$$ + +Now, consider the following two straightforward indefinite integrals: + +$$\begin{aligned} + \int \cos{x} \sin^2{x} \dd{x} + &= \:\:\,\, \frac{1}{3} \sin^3{x} + \\ + \int \cos^2{x} \sin{x} \dd{x} + &= -\frac{1}{3} \cos^3{x} +\end{aligned}$$ + +Applying these to our integral over $$\theta$$, the expression is reduced to just: + +$$\begin{aligned} + \int_\Omega \vb{E}_i(\vb{r}) \dd{\vb{r}} + &= \frac{|\vb{p}_i|}{12 \pi \varepsilon_0} \int_0^{2 \pi} + \begin{bmatrix} + \sin^3{\theta} \cos{\varphi} \\ + \sin^3{\theta} \sin{\varphi} \\ + \cos^3{\theta} + \end{bmatrix}_0^\pi + \dd{\varphi} + \\ + &= - \frac{|\vb{p}_i|}{6 \pi \varepsilon_0} \int_0^{2 \pi} + \begin{pmatrix} + 0 \\ + 0 \\ + \:1\: + \end{pmatrix} + \dd{\varphi} + \\ + &= - \frac{\vb{p}_i}{3 \varepsilon_0} +\end{aligned}$$ + +Inserting this result into the macroscopic field $$\vb{E}$$, +and recognizing the second term as the linear polarization density $$\vb{P}$$, +we arrive at the key result: + +$$\begin{aligned} + \vb{E} + = \vb{E}_\mathrm{loc} + - \frac{1}{3 \varepsilon_0} \sum_i \frac{\vb{p}_i}{\Omega} + \qquad \implies \qquad + \boxed{ + \vb{E}_\mathrm{loc} + = \vb{E} + \frac{1}{3 \varepsilon_0} \vb{P} + } +\end{aligned}$$ + +Whereas the individual dipoles are polarized by $$\vb{E}_\mathrm{loc}$$, +the macroscopic polarization density is defined from $$\vb{E}$$, +so we now know that: + +$$\begin{aligned} + \vb{P} + = \varepsilon_0 \chi_e \vb{E} + = \varepsilon_0 N \alpha \vb{E}_\mathrm{loc} + = \varepsilon_0 N \alpha \bigg( \vb{E} + \frac{1}{3 \varepsilon_0} \vb{P} \bigg) +\end{aligned}$$ + +Isolating this equation for $$\vb{P}$$, +and using that $$\vb{P} = \varepsilon_0 \chi_e \vb{E}$$, +we get a more accurate expression for the electric susceptibility $$\chi_e$$: + +$$\begin{aligned} + \boxed{ + \chi_e + = \frac{N \alpha}{1 - N \alpha / 3} + } +\end{aligned}$$ + +Notice that for $$N \alpha \ll 1$$ this reduces to our earlier naive estimate: +if each dipole's neighbors are far away, they do not provide much shielding. + +The corresponding macroscopic [dielectric function](/know/concept/dielectric-function/) +$$\varepsilon_r$$ is given by: + +$$\begin{aligned} + \boxed{ + \varepsilon_r + = 1 + \chi_e + = \frac{3 + 2 N \alpha}{3 - N \alpha} + } +\end{aligned}$$ + +Experimentally, $$\varepsilon_r$$ can be measured directly, but $$\alpha$$ cannot. +By isolating $$\varepsilon_r$$ for $$N \alpha$$, +we finally arrive at the **Clausius-Mossotti relation** for calculating $$\alpha$$: + +$$\begin{aligned} + \boxed{ + \frac{1}{3} N \alpha + = \frac{\varepsilon_r - 1}{\varepsilon_r + 2} + } +\end{aligned}$$ + +Since many theoretical models only calculate $$\alpha$$ +(e.g. the [Lorentz oscillator model](/know/concept/lorentz-oscillator-model/)), +this result is useful for relating theory to experimental results. + + + +## References +1. M. Fox, + *Optical properties of solids*, 2nd edition, + Oxford. +2. D.E. Aspnes, + [Local-field effects and effective-medium theory: a microscopic perspective](https://doi.org/10.1119/1.12734), + 1982, American Journal of Physics 50. +3. A. Zangwill, + *Modern Electrodynamics*, + Cambridge. +4. D.J. Griffiths, + *Introduction to Electrodynamics*, 5th edition, + Cambridge. diff --git a/source/know/concept/lorentz-oscillator-model/index.md b/source/know/concept/lorentz-oscillator-model/index.md index 61bbf6b..580ba99 100644 --- a/source/know/concept/lorentz-oscillator-model/index.md +++ b/source/know/concept/lorentz-oscillator-model/index.md @@ -61,20 +61,22 @@ The polarization density $$\vb{P}(t)$$ is therefore as shown below, where $$N$$ is the number of atoms per unit of volume. Note that the dipole moment vector $$\vb{p}$$ is defined as pointing from negative to positive, -whereas the electric field $$\vb{E}$$ goes from positive to negative: +whereas the electric field $$\vb{E}$$ points from positive to negative: $$\begin{aligned} \vb{P}(t) - = N \vb{p}(t) + \approx N \vb{p}(t) = N q \vb{x}(t) = \frac{N q^2}{m (\omega_0^2 - \omega^2 - i \gamma \omega)} \vb{E}(t) \end{aligned}$$ +Also note that $$\vb{P}$$ is not equal to $$N \vb{p}$$; +this will be clarified later. From the definition of the electric displacement field $$\vb{D} = \varepsilon_0 \vb{E} + \vb{P} = \varepsilon_0 \varepsilon_r \vb{E}$$, -we find that the material's +we see that the material's [dielectric function](/know/concept/dielectric-function/) -$$\varepsilon_r(\omega)$$ is given by: +$$\varepsilon_r(\omega)$$ must be given by: $$\begin{aligned} \boxed{ @@ -84,7 +86,7 @@ $$\begin{aligned} \end{aligned}$$ You may recognize the Drude model's plasma frequency $$\omega_p$$ here, -but the concept of plasma oscillation does not apply +but the concept of plasma oscillation does not apply, because there are no conduction electrons. When the light's driving frequency $$\omega$$ is far from the resonance $$\omega_0$$, @@ -108,23 +110,28 @@ $$\begin{aligned} In reality, atoms have multiple spectral lines, so we should treat them as if they have multiple oscillators -with different resonances $$\omega_\nu$$. +with different resonances $$\omega_n$$. In that case, the relative permittivity $$\varepsilon_r$$ becomes: - $$\begin{aligned} \boxed{ \varepsilon_r(\omega) - = 1 + \frac{N q^2}{\varepsilon_0 m} \sum_{\nu} \frac{1}{(\omega_\nu^2 - \omega^2 - i \gamma_\nu \omega)} + = 1 + \frac{N q^2}{\varepsilon_0 m} \sum_{n} \frac{1}{(\omega_n^2 - \omega^2 - i \gamma_n \omega)} } \end{aligned}$$ This gives $$\varepsilon_r$$ the shape of a staircase, -descending from low to high $$\omega$$ in clear steps at each $$\omega_\nu$$. +descending from low to high $$\omega$$ in clear steps at each $$\omega_n$$. Around each such resonance there is a distinctive "squiggle" in $$\Real\{\varepsilon_r\}$$ corresponding to a peak in the material's reflectivity, and there is an absorption peak in $$\Imag\{\varepsilon_r\}$$. -The damping from $$\gamma_\nu$$ broadens those peaks and reduces their amplitude. +The damping from $$\gamma_n$$ broadens those peaks and reduces their amplitude. + +Finally, recall that $$\vb{P}$$ was not exactly equal to $$N \vb{p}$$. +This is because each atomic dipole generates its own electric field, +affecting the response of its neighbors. +There exists a formula to correct for this effect: +the [Clausius-Mossotti relation](/know/concept/clausius-mossotti-relation/). diff --git a/source/know/concept/step-index-fiber/index.md b/source/know/concept/step-index-fiber/index.md index 2d049a1..e80480b 100644 --- a/source/know/concept/step-index-fiber/index.md +++ b/source/know/concept/step-index-fiber/index.md @@ -147,7 +147,7 @@ and check if we can then arrive at a non-trivial $$\Phi$$ for each case. &&= B \end{alignedat}$$ - $$B$$ can be nonzero, so this a valid solution. + $$B$$ can be nonzero, so this is a valid solution. We conclude that $$\ell^2 = 0$$ is the ground state. * For $$\ell^2 > 0$$, all solutions have the form |