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We characterize the effect of quantum interference on the line shapes andmeasured line positions in atomic spectra. These effects, which occur when theexcited state splittings are of order the excited state line widths, representan overlooked but significant systematic effect. We show that excited stateinterference gives rise to non-Lorenztian line shapes that depend on excitationpolarization, and we present expressions for the corrected line shapes. Wepresent spectra of 6,7 Li D lines taken at multiple excitation laserpolarizations and show that failure to account for interference changes theinferred line strengths and shifts the line centers by as much as 1 MHz. Usingthe correct lineshape, we determine absolute optical transition frequencieswith an uncertainty of <= 25kHz and provide an improved determination of thedifference in mean square nuclear charge radii between 6 Li and 7 Li. Thisanalysis should be important for a number of high resolution spectralmeasurements that include partially resolvable atomic lines.

Quantum interference and light polarization effects in unresolvable atomic lines: application to a precise measurement of the 6,7 Li D2 lines