Collision-induced absorption satellites

Information concerning the interaction potentials of Cs (7S, 5D)-rare gas pairs is obtained by interpreting the temperature dependence of the 6S-7S,5D far wing and satellite profiles. A sensitive laser fluorescence technique is used to obtain the absorption coefficient of the mixture. The collision induced oscillator strength, a rapidly varying function of the interatomic distance in the case of such forbidden transitions, is also deduced. Experimental potentials and oscillator strengths are compared with available calculated values. 

In addition to LIF resonant two-photon ionization (Sect. 1.4) can also be used for the sensitive detection of collision-induced rotational transitions. This method represents an efficient alternative to LIF for those electronic states that do not emit detectable fluorescence because there are no allowed optical transitions into lower states. An illustrative example is the detailed investigation of inelastic collisions between excited N2 molecules and different collision partners [995]. A vibration-rotation level (v, J ) in the a Jig state of N2 is selectively populated by two-photon absorption (Fig. 8.10). The collision-induced transitions to other levels v + An, / + AJ) are monitored by resonant two-photon ionization (REMPI, Sect. 1.2) with a pulsed dye laser. The achievable good signal-to-noise ratio is demonstrated by the collisional satellite spectrum in Fig. 8.10b, where the optically pumped level was v = 2, J = 7). This level is ionized by the P(l) parent line in the spectrum, which has the signal height 7.25 on the scale of Fig. 8.10b. 

While collision-induced transitions in excited electronic states can be monitored through the satellite lines in the fluorescence spectrum (Sect. 8.2.2), inelastic collisional transfer in electronic ground states of molecules can be studied by changes in the absorption spectrum. This technique is particularly advantageous if the radiative lifetimes of the investigated rotational-vibrational levels are so long that fluorescence detection fails because of intensity problems. 

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