Physical Approximations and Domains of Validity

Key physical approximations, their domains of validity, and failure modes.

Approximation

Mathematical form

Domain of validity

Failure mode

Within-Shell Isolation (\(\Delta n = 0\))

\(V_E = \mathrm{diag}_n(V_E)\), no \(n \to n\!\pm\!1\) coupling

Stark shift \(\ll\) shell spacing \(2Z^2\mathrm{Ry}/n^3\)

Quadratic Stark; Inglis-Teller merging at \(N_e \gtrsim 10^{24}\) m-3.

Quasi-Static Ion Microfields

\(\vec{F}_\mathrm{ion} = \mathrm{const}\)

Fluctuation rate \(\nu_i \ll\) Stark width \(\Delta E_S\)

Ion dynamics / motional narrowing; use FFM.

Semi-Classical Electron Impact

Lorentzian with GBK width \(\gamma_e\)

\(\lambda_{dB} \ll\) impact parameter \(\rho\)

Quantum close-coupling needed for cold dense plasmas.

Dipole Approximation

\(V_\mathrm{rad} \propto \vec{r}\cdot\vec{E}\)

\(\lambda \gg \langle r\rangle_n \sim n^2 a_0/Z\)

Quadrupole/octupole for high-\(n\) Rydberg states.