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Energy-loss near-edge structure is the detailed shape near an inner-shell excitation edge in an electron energy loss spectroscopy measurement. Transition probabilities sample accessible unoccupied electronic states, so local bonding and orientation affect the edge shape as well as elemental identity.

Comparing two specimens containing the same element can therefore reveal different electronic environments. Interpretation must account for instrumental energy resolution, the incident beam's energy spread and lifetime broadening of the states involved. ^[ref] A small peak difference alone does not uniquely determine one atomic arrangement.

A line with lifetime broadening has a Lorentzian line shape. Write its half-width at half-maximum in angular-frequency units as $\kappa >0$. The Wiener-Khinchin theorem, or the Fourier transform of the Lorentzian, givesTherefore in vacuumThe sketch is a cosine fringe pattern about baseline $I_0$, bounded by $I_0[1\pm e^{-\sqrt{2}\kappa |y|/c}]$. Its central value is $2I_0$, its spatial interference fringe spacing is $\lambda /\sqrt{2}$, and its visibility decays on length $c/(\sqrt{2}\kappa )$. For an isolated transition whose population lifetime is $T_1$ and which has no extra dephasing, $\kappa =1/(2T_1)$, so the field coherence time is $2T_1$, not $T_1$. Introducing $\kappa$ avoids confusing population, wave amplitude and spectral-width conventions when no numerical linewidth is given.

Use $u$ as a spectroscopic wavenumber, in the same units throughout. Write the mass absorption coefficient of the absorbing species asHere $S$ is the spectral line strength, the integrated mass absorption coefficient; it is not the line-centre coefficient. If ${\kappa }_{\nu }$ has units ${\mathrm{m}}^2\mathrm{k}{\mathrm{g}}^{-1}$ and $\nu$ is in $\mathrm{c}{\mathrm{m}}^{-1}$, then $S$ has units ${\mathrm{m}}^2\mathrm{k}{\mathrm{g}}^{-1}\mathrm{c}{\mathrm{m}}^{-1}$. For absorber mass density ${\rho }_a$, the volume coefficient in Beer-Lambert law is ${\rho }_a{\kappa }_{\nu }$.

Lifetime broadening. Finite lifetimes of the upper and lower states destroy optical coherence, even for an isolated molecule. Exponential coherence decay gives a Lorentzian line shape. For population decay rates ${\Gamma }_u,{\Gamma }_l$ and no extra dephasing, its wavenumber half-width is $({\Gamma }_u+{\Gamma }_l)/(4\pi c)$, with $c$ expressed in the length unit reciprocal to $\nu$. This sets a natural linewidth and can matter at extremely low collision rates; it is generally much smaller than atmospheric collisional or thermal widths.

Thermal Doppler broadening. A Maxwell-Boltzmann distribution of molecular line-of-sight velocities givesThis Gaussian distribution has a $1/e$ half-width ${\Delta }_D$, determined by absorber molecular mass $m_a$ and temperature. It is especially relevant in the rarefied upper atmosphere, where collisions are infrequent.

Pressure broadening. Collisions perturb transition frequencies and phases. In the impact regime, exponential phase decorrelation givesHere ${\Delta }_L$ is the half-width at half maximum, proportional to the coherence-destroying collision rate. It depends on perturber density, molecular collision properties, and temperature; it is often parameterized by ${\Delta }_L\propto p(T_{\ast }/T{)}^{n_T}$ for a specified broadener. It dominates much of the dense lower atmosphere. The Lorentzian line shape has algebraic $\delta {\nu }^{-2}$ wings, whereas the Doppler profile has rapidly decreasing Gaussian wings. Where both mechanisms matter, their convolution is a Voigt profile. A pure pressure-broadened profile should not be extrapolated to arbitrarily low pressure while discarding the finite Doppler core.

The finite width of a spectral line can arise from finite optical coherence or a distribution of resonance frequencies. lifetime broadening and impact-regime pressure broadening often give Lorentzian line shapes; thermal Doppler broadening gives a Gaussian component. The instrument response must also be included when interpreting a measured spectrum.

temperature can smear measured spectral or transport features through the spread of occupied energies and through temperature-dependent scattering. Fermi-edge occupation broadening and phonon-induced lifetime broadening are different mechanisms and should not be equated.