Two-photon-absorption line strengths for nitric oxide: Comparison of theory and sub-Doppler, laser-induced fluorescence measurements

We discuss the results of high-resolution, sub-Doppler two-photon-absorption laser-induced fluorescence (TPALIF) spectroscopy of nitric oxide at lowpressure and room temperature. The measurements were performed using the single-longitudinal mode output of a diode-laser-seeded optical parametric generator (OPG) system with a measured frequency bandwidth of 220 MHz. The measurements were performed using a counter-propagating pump beam geometry, resulting in sub-Doppler TPALIF spectra of NO for various rotational transitions in the (0,0) vibrational band of the A(2)Sigma(+) -X-2 Pi electronic transition. The experimental results are compared with the results of a perturbative treatment of the rotational line strengths for the 20 different rotational branches of the X-2 Pi (v 0 0 = 0) ! A2 + +(v 0 = 0) two-photon absorption band. In the derivation of the expressions for the two-photon transition absorption strength, the closure relation is used for rotational states in the intermediate levels of the two-photon transition in analogy with the Placzek treatment of Raman transitions. The theoretical treatment of the effect of angular momentum coupling on the two-photon rotational line strengths features the use of irreducible spherical tensors and 3j symbols. The final results are expressed in terms of the Hund's case (a) coupling coefficients aJ and bJ for the X-2 Pi (v 0 0 = 0) rotational level wavefunctions, which are intermediate between Hund's case (a) and case (b). Considerable physical insight is provided by this final form of the equations for the rotational line strengths. Corrections to the two-photon absorption rotational line strength for higher order effects such as centrifugal stretching can be included in a straightforward fashion in the analysis by incorporating higher order terms in these coupling coefficients aJ and bJ, although these corrections are essentially negligible for J < 50. The theoretical calculations of relative line intensities are in good agreement both with our experiment and with published experimental results. In addition, the calculated line shapes and relative intensities for closely spaced main branch and satellite transitions are in excellent agreement with our experimental measurements. Published by AIP Publishing.