Laboratory measurements and theoretical calculations of O_2 A band electric quadrupole transitions

Abstract

Frequency-stabilized cavity ring-down spectroscopy was utilized to measure electric quadrupole transitions within the ^(16)O_2 A band, b^1Σ^+_g ← X^3Σ^-_g(0,0). We report quantitative measurements (relative uncertainties in intensity measurements from 4.4% to 11%) of nine ultraweak transitions in the ^NO, ^PO, ^RS, and ^TS branches with line intensities ranging from 3×10^(−30) to 2×10^(−29) cm molec.^(−1). A thorough discussion of relevant noise sources and uncertainties in this experiment and other cw-cavity ring-down spectrometers is given. For short-term averaging (t<100 s), we estimate a noise-equivalent absorption of 2.5×10^(−10) cm^(−1) Hz^(−1/2). The detection limit was reduced further by co-adding up to 100 spectra to yield a minimum detectable absorption coefficient equal to 1.8×10^(−11) cm^(−1), corresponding to a line intensity of ~2.5×10^(−31) cm molec.^(−1). We discuss calculations of electric quadrupole line positions based on a simultaneous fit of the ground and upper electronic state energies which have uncertainties <3 MHz, and we present calculations of electric quadrupole matrix elements and line intensities. The electric quadrupole line intensity calculations and measurements agreed on average to 5%, which is comparable to our average experimental uncertainty. The calculated electric quadrupole band intensity was 1.8(1)×10^(−27) cm molec.−1 which is equal to only ~8×10^(−6) of the magnetic dipole band intensity.

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