Fine structure

Interference fringes, showing fine structure (splitting) of a cooled deuterium source, viewed through a Fabry-Pérot étalon.

In atomic physics, the fine structure describes the splitting of the spectral lines of atoms due to electron spin and relativistic corrections to the non-relativistic Schrödinger equation.

The gross structure of line spectra is the line spectra predicted by the quantum mechanics of non-relativistic electrons with no spin. For a hydrogenic atom, the gross structure energy levels only depend on the principal quantum number n. However, a more accurate model takes into account relativistic and spin effects, which break the degeneracy of the energy levels and split the spectral lines. The scale of the fine structure splitting relative to the gross structure energies is on the order of (Zα)², where Z is the atomic number and α is the fine-structure constant, a dimensionless number equal to approximately $1/137$.

The fine structure energy corrections can be obtained by using perturbation theory. To do this one adds three corrective terms to the Hamiltonian: the leading order relativistic correction to the kinetic energy, the correction due to the spin-orbit coupling, and the Darwinian term. The full Hamiltonian is given by

$H=H_{0}+H_{\mathrm{kinetic}}+H_{\mathrm{so}}+H_{\mathrm{Darwinian}},\!$

where $H_{0}$ is the Hamiltonian from the Coulomb interaction. These corrections can also be obtained from the non-relativistic limit of the Dirac equation, since Dirac's theory naturally incorporates relativity and spin interactions.

Kinetic energy relativistic correction

Classically, the kinetic energy term of the Hamiltonian is

$T = \frac{p^{2}}{2m},$

where $p$ is the momentum and $m$ is the mass of the electron.

However, when considering a more accurate theory of nature viz. special relativity, we must use a relativistic form of the kinetic energy,

$T = \sqrt{p^{2}c^{2} + m^{2}c^{4}} - mc^{2},$

where the first term is the total relativistic energy, and the second term is the rest energy of the electron. ($c$ is the speed of light) Expanding this in a Taylor series ( specifically a binomial series ), we find

$T = \frac{p^{2}}{2m} - \frac{p^{4}}{8m^{3}c^{2}} + \cdots.$

Then, the first order correction to the Hamiltonian is

$H_{\mathrm{kinetic}} = -\frac{p^{4}}{8m^{3}c^{2}}.$

Using this as a perturbation, we can calculate the first order energy corrections due to relativistic effects.

$E_n^{(1)} = \left\langle\psi^0\right\vert H' \left\vert\psi^0\right\rangle = -\frac{1}{8m^3c^2}\left\langle\psi^0\right\vert p^4 \left\vert\psi^0\right\rangle = -\frac{1}{8m^3c^2}\left\langle\psi^0\right\vert p^2 p^2 \left\vert\psi^0\right\rangle$

where $\psi^{0}$ is the unperturbed wave function. Recalling the unperturbed Hamiltonian, we see

$\begin{align} H^{0}\left\vert\psi^{0}\right\rangle &= E_{n}\left\vert\psi^{0}\right\rangle \\ \left(\frac{p^{2}}{2m} + V\right)\left\vert\psi^{0}\right\rangle &= E_{n}\left\vert\psi^{0}\right\rangle \\ p^{2}\left\vert\psi^{0}\right\rangle &= 2m(E_{n} - V)\left\vert\psi^{0}\right\rangle \end{align}$

We can use this result to further calculate the relativistic correction:

$\begin{align} E_n^{(1)} &= -\frac{1}{8m^3 c^2}\left\langle\psi^0\right\vert p^2 p^2 \left\vert\psi^{0}\right\rangle \\ E_n^{(1)} &= -\frac{1}{8m^3 c^2}\left\langle\psi^0\right\vert (2m)^2 (E_n - V)^2\left\vert\psi^0\right\rangle \\ E_n^{(1)} &= -\frac{1}{2mc^2}\left(E_n^2 - 2E_n\langle V\rangle + \left\langle V^2\right\rangle \right) \end{align}$

For the hydrogen atom, $V(r) = \frac{-e^2}{4\pi \varepsilon_0 r}$, $\left\langle \frac{1}{r} \right\rangle = \frac{1}{a_0 n^2}$, and $\left\langle \frac{1}{r^2} \right\rangle = \frac{1}{(l + 1/2)n^{3}a_{0}^{2}}$ where $a_{0}$ is the Bohr Radius, $n$ is the principal quantum number and $l$ is the azimuthal quantum number. Therefore the first order relativistic correction for the hydrogen atom is

$\begin{align} E_{n}^{(1)} &= -\frac{1}{2mc^2}\left(E_{n}^2 + 2E_n\frac{e^2}{4\pi \varepsilon_0}\frac{1}{a_0 n^2} + \frac{1}{4\pi \varepsilon_0}\frac{e^4}{(l + \frac{1}{2}) n^3 a_0^2}\right) \\ &= -\frac{E_n^2}{2mc^2}\left(\frac{4n}{l + \frac{1}{2}} - 3\right) \end{align}$

where we have used:

$E_n = - \frac{e^2}{8 \pi \varepsilon_0 a_0 n^2}$

On final calculation, the order of magnitude for the relativistic correction to the ground state is $-9.056 \times 10^{-4}\ \text{eV}$.

Spin-orbit coupling

For a hydrogen-like atom with $Z$ protons, orbital momentum $\vec L$ and electron spin $\vec S$, the spin-orbit term is given by:

$H_{so}=\frac{1}{2} \left(\frac{Ze^2}{4\pi \varepsilon_{0}}\right)\left(\frac{g_s}{2m_{e}^{2}c^{2}}\right)\frac{\vec L\cdot\vec S}{r^{3}}$

$m_e$ is the electron mass, $\varepsilon_0$ is the vacuum permittivity and $g_s$ is the spin g-factor. $r$ is the distance of the electron from the nucleus.

The spin-orbit correction can be understood by shifting from the standard frame of reference (where the electron orbits the nucleus) into one where the electron is stationary and the nucleus instead orbits it. In this case the orbiting nucleus functions as an effective current loop, which in turn will generate a magnetic field. However, the electron itself has a magnetic moment due to its intrinsic angular momentum. The two magnetic vectors, $\vec B$ and $\vec\mu_s$ couple together so that there is a certain energy cost depending on their relative orientation. This gives rise to the energy correction of the form

$\Delta E_{SO} = \xi (r)\vec L \cdot \vec S$

Notice that there is a factor of 2, called the Thomas precession, which comes from the relativistic calculation that changes back to the electron's frame from the nucleus frame.

Since

$\begin{align} \left\langle \frac{1}{r^3} \right\rangle &= \frac{Z^3}{n^3 a_0^3} \frac{1}{l \left(l + \frac{1}{2}\right) (l + 1)} \\ \left\langle \vec L \cdot \vec S \right\rangle &= \frac{\hbar^2}{2} [j(j + 1) - l(l + 1) - s(s + 1)] \end{align}$

the expectation value for the Hamiltonian is:

$\left\langle H_{SO} \right\rangle = \frac{E_n{}^2}{m_e c^2} ~n~ \frac{j(j + 1) - l(l + 1) - \frac{3}{4}}{l \left( l + \frac{1}{2}\right) (l + 1) }$

Thus the order of magnitude for the spin-orbital coupling is $\frac{Z^4}{n^3(j+1/2)} 10^{-5}\text{ eV}$.

Remark: On the (n,l,s)=(n,0,1/2) and (n,l,s)=(n,1,-1/2) energy level, which the fine structure said their level are the same. If we take the g-factor to be 2.0031904622, then, the calculated energy level will be different by using 2 as g-factor. Only using 2 as the g-factor, we can match the energy level in the 1st order approximation of the relativistic correction. When using the higher order approximation for the relativistic term, the 2.0031904622 g-factor may agree with each other. However, if we use the g-factor as 2.0031904622, the result does not agree with the formula, which included every effect.

Darwin term

There is one last term in the non-relativistic expansion of the Dirac equation. It is referred to as the Darwin, and it given by:

$\begin{align} H_{\mathrm{Darwinian}} &= \frac{\hbar^{2}}{8m_{e}^{2}c^{2}}\,4\pi\left(\frac{Ze^2}{4\pi \varepsilon_{0}}\right)\delta^{3}\left(\vec r\right) \\ \langle H_{\mathrm{Darwinian}} \rangle &= \frac{\hbar^{2}}{8m_{e}^{2}c^{2}}\,4\pi\left(\frac{Ze^2}{4\pi \varepsilon_{0}}\right)| \psi(0)|^2 \\ \psi (0) &= 0 \text{ for } l > 0 \\ \psi (0) &= \frac{1}{\sqrt{4\pi}}\,2 \left( \frac {Z}{n a_0} \right)^\frac {3}{2} \text{ for } l = 0 \\ H_{\mathrm{Darwinian}} &= \frac{2n}{m_e c^{2}}\,E_n^2 \end{align}$

The Darwin term affects only the s-orbit. This is because the wave function of an electron with $l > 0$ vanishes at the origin, hence the delta function has no effect. For example it gives the 2s-orbit the same energy as the 2p-orbit by raising the 2s-state by 9.057×10⁻⁵ eV.

The Darwin term changes the effective potential at the nucleus. It can be interpreted as a smearing out of the electrostatic interaction between the electron and nucleus due to zitterbewegung, or rapid quantum oscillations, of the electron. This can be motivated by a short calculation^[1]

Quantum fluctuations allow for the creation of virtual electron-positron pairs with a lifetime estimated by the uncertainty principle $\Delta t \approx \hbar/\Delta E \approx \hbar/mc^2$. The distance the particles can move during this time is $\xi \approx c\Delta t \approx \hbar/mc = \lambda_c$, the Compton wavelength. The electrons of the atom interact with those pairs. This yields a fluctuating electron position $\vec r + \vec \xi$. Using a Taylor expansion, the effect on the potential $U$ can be estimated:

$U(\vec r + \vec\xi) \approx U(\vec r) + \xi\cdot\nabla U(\vec r) + \frac12 \sum_{ij} \xi_i\xi_j \partial_i\partial_j U(\vec r)$

Averaging over the fluctuations $\vec \xi$

$\overline\xi = 0, \quad \overline{\xi_i\xi_j} = \frac13 \overline{\vec\xi^2} \delta_{ij},$

gives the average potential

$\overline{U\left(\vec r + \vec\xi\right)} = U\left(\vec r\right) + \frac{1}{6} \overline{\vec\xi^2} \nabla^2 U\left(\vec r\right).$

Approximating $\overline{\vec\xi^2} \approx \lambda_c^2$, this yields the perturbation of the potential due to fluctuations:

$\delta U \approx \frac16 \lambda_c^2 \nabla^2 U = \frac{\hbar^2}{6m^2c^2}\nabla^2 U$

To compare with the expression above, plug in the Coulomb potential:

$\nabla^2 U = -\nabla^2 \frac{Z e^2}{4\pi\varepsilon_0 r} = 4\pi \left(\frac{Z e^2}{4\pi\varepsilon_0}\right) \delta(\vec r) \quad\Rightarrow\quad \delta U \approx \frac{\hbar^2}{6m^2c^2} 4\pi \left(\frac{Z e^2}{4\pi\varepsilon_0}\right) \delta(\vec r)$

This is only slightly different.

Another mechanism that affects only the s-state is the Lamb shift, a further, smaller correction that arises in quantum electrodynamics that should not be confused with the Darwin term. The Darwin term gives the s-state and p-state the same energy, but the Lamb shift makes the s-state higher in energy than the p-state.

Total effect

The total effect, obtained by summing the three components up, is given by the following expression:^[2]

$\Delta E = \frac{E_{n}(Z\alpha)^{2}}{n}\left( \frac{1}{j + \frac{1}{2}} - \frac{3}{4n} \right)\,,$

where $j$ is the total angular momentum ($j = 1/2$ if $l = 0$ and $j = l \pm 1/2$ otherwise). It is worth noting that this expression was first obtained by A. Sommerfeld based on the old Bohr theory; i.e., before the modern quantum mechanics was formulated.

The total effect can also be obtained by using the Dirac equation. In this case, it is not necessary to treat the electron as non-relativistic or make other approximations. The exact energies are given by^[3]

$E_{j\,n} = -m_\text{e}c^2\left[1-\left(1+\left[\dfrac{\alpha}{n-j-\frac{1}{2}+\sqrt{\left(j+\frac{1}{2}\right)^2-\alpha^2}}\right]^2\right)^{-1/2}\right].$

This expression expands to first order to give the energy corrections derived from perturbation theory, but it contains all higher order terms that were left out in the other calculations. However, this equation does not contain the hyperfine structure corrections, which are due to interactions with the nuclear spin. Other corrections from quantum field theory such as the Lamb shift and the anomalous magnetic dipole moment of the electron are not included.

See also

• Spin-orbit interaction
• Angular momentum coupling
• Hyperfine structure

References

1. Zelevinsky, Vladimir (2011), Quantum Physics Volume 1: From Basics to Symmetries and Perturbations, WILEY-VCH, ISBN 978-3-527-40979-2 p. 551
2. Berestetskii, V. B.; E. M. Lifshitz; L. P. Pitaevskii (1982). Quantum electrodynamics. Butterworth-Heinemann. ISBN 978-0-7506-3371-0.
3. Sommerfeld, Arnold (1919). Atombau und Spektrallinien'. Braunschweig: Friedrich Vieweg und Sohn. ISBN 3-87144-484-7. German English

• Griffiths, David J. (2004). Introduction to Quantum Mechanics (2nd ed.). Prentice Hall. ISBN 0-13-805326-X.
• Liboff, Richard L. (2002). Introductory Quantum Mechanics. Addison-Wesley. ISBN 0-8053-8714-5.

External links

• Hyperphysics: Fine Structure
• University of Texas: The fine structure of hydrogen