Two-color polarization spectroscopy measurements of Zeeman state-to-state collision induced transitions of nitric oxide in binary gas mixtures

Abstract

We investigated collision induced transitions in the (0, 0) band of the A2Σ+–X2Π electronic transition of nitric oxide (NO) using two-color polarization spectroscopy (TCPS). Two sets of TCPS spectra for 1% NO, diluted in different buffer gases at 295 K and 1 atm, were obtained with the pump beam tuned to the R11(11.5) and OP12(1.5) transitions. The buffer gases were He, Ar, and N2. The probe was scanned while the pump beam was tuned to the line center. Theoretical TCPS spectra, calculated by solving the density matrix formulation of the time-dependent Schrödinger wave equation, were compared with the experimental spectra. A collision model based on the modified exponential-gap law was used to model the rotational level-to-rotational level collision dynamics. A model for collisional transfer from an initial to a final Zeeman state was developed based on the difference in cosine of the rotational quantum number J projection angle with the z-axis for the two Zeeman states. Rotational energy transfer rates and Zeeman state collisional dynamics were varied to obtain good agreement between theory and experiment for the two different TCPS pump transitions and for the three different buffer gases. One key finding, in agreement with quasi-classical trajectory calculations, is that the spin-rotation changing transition rate in the A2Σ+ level of NO is almost zero for rotational quantum numbers ≥8. It was necessary to set this rate to near zero to obtain agreement with the TCPS spectra.