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I am a beginner at QFT, and I've been looking through the questions on this site (such as this one and this one) but I've not found one that satisfactorily answers the question of how to reproduce the calculations of energy levels of atoms from a priori QFT. Essentially, I haven't seen any calculation of spectral series directly from QFT; everything I've seen comes from tiny QFT corrections such as the Lamb shift, with the primary spectra still solved using the Schrodinger equation.

Based on my knowledge (which is admittedly limited), I imagine that the process would look something like this. The wavefunction of the electron would need to be replaced by single-particle states $|p\rangle$, which you'd need to Fourier transform to get the position representation. The non-relativistic Coulombic interaction would be replaced by a tree-level Feynman diagram of the exchange of a photon between two fermions of opposite charge (proton & electron), but I'm not sure what the equivalent would be if we apply relativistic QFT. The ground-state energy could be obtained by taking $\langle 0 | \hat H |0\rangle$, but I'm not sure how we could do the same with the excited states. Or perhaps this is the wrong approach and I should start from the Bethe–Salpeter equation instead.

Ignore why you'd want to use the clearly overkill tools of QFT to perform, for instance, the calculation of the spectral series of hydrogen. How would one go about doing it, 100% in the framework of QFT?

Qmechanic
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1 Answers1

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Computing QED corrections to the hydrogen atom in a fully relativistic two-particle formalism is messy; in principle, it could be done starting from the Bethe-Salpeter equation, in practice, it is very hard.

If you take the nuclear mass to be infinite in a first approximation, then the effect of the nucleus (as an external Coulomb potential) can be built into your fermion creation/annihilation operators: $$ \Psi(x)=\sum_{\substack{n \\ E_n>0}}a_n\psi_n(x)+\sum_{\substack{n \\ E_n<0}}b^\dagger_n\psi_n(x) \ , $$ where $\psi_n(x)=\phi_n(\vec{r})\exp(-iE_nt)$ are solutions of the (first-quantized) Dirac equation: $$ \left[\vec{\alpha}\cdot\vec{p}+\beta m-|e|\int\mathrm{d}^3r'\frac{\rho_\text{N}(\vec{r}{}')}{4\pi|\vec{r}-\vec{r}{}'|}I\right]\phi_n(\vec{r})=E_n\phi_n(\vec{r}) \ . $$ This defines the so-called Furry representation. For a point-like nucleus $$ -|e|\int\mathrm{d}^3r'\frac{\rho_\text{N}(\vec{r}{}')}{4\pi|\vec{r}-\vec{r}{}'|}=-\frac{Z\alpha}{r} \ , $$ and the Dirac equation can be solved analytically. Then you can set up the fermion propagator, the diagram rules, and go on almost like in the non-interacting case.

Using these solutions, the QED corrections to the atomic energy levels can be obtained from e.g. the Gell-Mann - Low (GML) formula, which relates the energy shift to $S$-matrix elements. In leading (one-loop) order, two $S$-matrix diagrams contribute, belonging to bound-electron self-energy (with a mass counterterm understood) and vacuum polarization:

The double lines correspond to the fermion propagator in the external Coulomb field of the nucleus. You can process these diagrams to a certain degree, but their exact evaluation can only be done numerically. If your system is predominantly non-relativistic (like the hydrogen atom), then you can start doing expansions in the binding parameter $Z\alpha$, and this will lead you to the ${\cal{O}}(m\alpha(Z\alpha)^4, \, m\alpha(Z\alpha)^4\ln(Z\alpha))$ textbook result for the Lamb shift (see e.g. Ch. 15 of The Theory of Photons and Electrons by Jauch & Rohrlich); the expectation value of the Uehling potential is a tiny part of this shift, originating from the second diagram. For strongly relativistic systems (hydrogen-like ions with large $Z$), you have no choice but to calculate the fully relativistic expressions numerically, but that is very difficult; see e.g. this review by Mohr, Plunien and Soff to get a taste, and for a discussion on the GML formula. If you already calculate everything fully numerically, than the assumption of a point-like nucleus is not that important, and you can incorporate some finite density model.

Treating the nucleus explicitly as a particle is possible for a spin $1/2$ nucleus, but for other nuclear spins, I am not sure if there is even a rigorous first-principles theory (there is possibly one for spin $0$, but for higher spins, there are most likely only effective theories working with non-relativistic wave functions). Recoil corrections can be extracted from Coulomb and transverse photon exchange diagrams in the Bethe-Salpeter formalism; in the low-energy approximation, these contribute to the QED energy shift at ${\cal{O}}(m(Z\alpha)^5(m/M))$ (there is no $\alpha$ here, only $Z\alpha$, signalling that these are non-radiative QED effects, not loop corrections).