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A spectral line has finite width when the emitted or absorbed field loses coherence, or when different emitters have different transition frequencies. It is useful to distinguish homogeneous spectral broadening of each emitter from inhomogeneous spectral broadening across the ensemble.

Finite lifetime and dephasing. For an upper-state population lifetime $\tau$ and a stable lower state, the radiating amplitude decays as $e^{-t/(2\tau )}$. Its Fourier spectrum is Lorentzian, with full width at half maximumMore generally, an optical coherence time $T_2$ gives $\Delta {\omega }_{\mathrm{hom}}=2/T_2$. Both level lifetimes and pure dephasing can contribute to $1/T_2$. Distinguishing population lifetime from amplitude coherence time prevents the usual factor-of-two error.

Thermal motion. To first order in velocity, $\delta \nu ={\nu }_0{v}_{\parallel }/c$. A Maxwell-Boltzmann velocity distribution therefore produces a Gaussian profile, withThis is inhomogeneous doppler broadening: different velocity classes have different resonance frequencies. A distribution of bulk velocities can add further broadening, while a common bulk velocity shifts the line.

Interactions with the surroundings. Collisions can interrupt the dipole wave phase and perturb the energy levels, producing pressure broadening and shifts. In the impact approximation, approximately exponential wave phase relaxation produces a Lorentzian contribution; its rate increases with perturber density times an appropriate velocity-averaged collision cross section. Slowly varying electric microfields can instead produce non-Lorentzian Stark profiles. Neutral perturbers, charged perturbers and resonance interactions need not produce the same line shape. These mechanisms and the Gaussian thermal limit are distinguished in NIST's atomic-spectroscopy compendium.^[ref]

Finite observation time limits coherence; transit-time broadening also occurs for particles crossing a narrow optical beam. Strong resonant excitation causes power broadening: for an ideal lifetime-limited two-level transition, $\Delta \omega =\Gamma \sqrt{1+s}$ with population decay rate $\Gamma$ and saturation parameter $s$. Unresolved fine structure, hyperfine structure, isotope components, or spatially varying Zeeman and Stark shifts may look like a single broadened feature even though several frequencies are present.

The observed spectrum is additionally convolved with the instrument response. A Gaussian Doppler contribution convolved with Lorentzian homogeneous broadening gives a Voigt profile; their full widths do not generally add in quadrature. An informative experiment varies temperature, perturber pressure and excitation intensity separately, calibrates the spectrometer response with a narrower reference, and checks optical thickness or self-absorption. Extrapolation to weak excitation and low pressure helps isolate the lifetime contribution, while a Doppler-free technique is needed if velocity spread still dominates.