Date of Award
Doctor of Philosophy (PhD)
Department of Engineering Physics
David E. Weeks, PhD.
Recent interest in optically-pumped alkali laser systems has prompted this study into the binary interaction potentials between species of alkali-metal and rare-gas atoms and the effects of the collision of these species on the alkali-metal atom absorption spectrum. Special attention is placed on the relationship of the interaction potentials and the resulting line shape. The X2Σ+1/2, A2π1/2, A2π3/2, and B2Σ+1/2 potential energy curves and associated dipole matrix elements are computed for M+ Ng at the spin-orbit multi-reference configuration interaction level, where M = K, Rb, Cs and Ng = He, Ne, Ar. Dissociation energies and equilibrium positions for all minima are identified and corresponding vibrational energy levels are computed. Difference potentials are used together with the quasistatic approximation to estimate the position of satellite peaks of collisionally broadened D2 lines. The comparison of potential energy curves for different alkali-metal atom and noble-gas atom combinations is facilitated by using the same level of theory for all nine M + Ng pairs. The Anderson-Talman theory of spectral line broadening is used together with potential energy curves calculated at the spin-orbit multi-reference configuration interaction level to compute broadening, shifting, and asymmetry coefficients of the D1 and D2 lines. The calculated coefficients are compared to experiment for a variety of temperatures. In all cases general agreement is observed for the broadening coefficients, while significant disagreement is observed for the shifting coefficients. I also compare my K + He broadening and shifting results with fully quantum mechanical calculations that employ the Baranger theory of collisional line broadening, and then compare the results with other semiclassical calculations. As with the comparison to experiment, closer agreement is observed for the broadening coefficients while the shifting coefficients exhibit significant disagreement. I use the natural variation between the difference potentials of the nine M + Ng pairs to explore the relationship between potential and line shape as determined by Anderson-Talman theory and develop a picture for the mechanism that underlies the general agreement between theoretical and experimental results on the broadening coefficient and the general disagreement on shifting coefficients.
DTIC Accession Number
Blank, Larry A., "Potential Energy Curves and Associated Line Shape of Alkali-Metal and Noble-Gas Interactions" (2014). Theses and Dissertations. 1.