Collisional polarization transfer

The results obtained so far with collisional energy-transfer spectroscopy are restricted to excited sodium atoms A = Na(32/,3/2) and quenching by a variety of simple polar and nonpolar molecules. The technique is applicable to any vaporizable molecule and will be available for a number of other atoms as well in due course with the progress of laser technology. The E-V-R transfer processes from and to sodium atoms have a number... 

The rotational dynamics of nitrogen and carbon dioxide were recorded by Akhmanov and Koroteev [7]. The transients look similar to the transients by Morgen et al. [8], recorded with time resolved Raman induced polarization spectroscopy [9]. A fs-DFWM experiment was performed by Frey et al. [10] on diatomics and linear polyatomics. To prevent collisional dephasing, they transferred the method into the expansion zone of a molecular beam. In succession, experiments on linear molecules and symmetric tops were performed on molecules like CHCI3 [11] and CgHf, [12], Transients of asymmetric tops like the near oblate pyrimidine, pyrazine and pyridine [13] and SO2 [11] were reported in the following years. 

Of a special astronomical interest is the absorption due to pairs of H2 molecules which is an important opacity source in the atmospheres of various types of cool stars, such as late stars, low-mass stars, brown dwarfs, certain white dwarfs, population III stars, etc., and in the atmospheres of the outer planets. In short absorption of infrared or visible radiation by molecular complexes is important in dense, essentially neutral atmospheres composed of non-polar gases such as hydrogen. For a treatment of such atmospheres, the absorption of pairs like H-He, H2-He, H2-H2, etc., must be known. Furthermore, it has been pointed out that for technical applications, for example in gas-core nuclear rockets, a knowledge of induced spectra is required for estimates of heat transfer [307, 308]. The transport properties of gases at high temperatures depend on collisional induction. Collision-induced absorption may be an important loss mechanism in gas lasers. Non-linear interactions of a supermolecular nature become important at high laser powers, especially at high gas densities. 

Let us first discuss a system which is traditional for optical pumping in the Kastler sense [106, 224, 226], namely an optically oriented alkali atom A (see Fig. 1.1) in a noble gas X buffer surrounding. It is important to take into account the fact that in alkali atoms, owing to hyperfine interaction, nuclear spins are also oriented. However, in a mixture of alkali vapor with a noble gas alkali dimers A2 which are in the 1SJ electronic ground state are always present. There exist two basic collisional mechanisms which lead to orientation transfer from the optically oriented (spin-polarized) atom A to the dimer A2 (a) creation and destruction of molecules in triple collisions A + A + X <—> A2 + X (6) exchange atom-dimer reaction... 

PTR-MS combines the concept of Cl with the swarm technique of the flow tube and flow-drift-tube mentioned above. In a PTR-MS instrument, we apply a Cl system which is based on proton-transfer reactions, and preferentially use HsO" " as the primary reactant ion. As discussed earlier, HsO" " is a most suitable primary reactant ion when air samples containing a wide variety of trace gases or VOCs are to be analyzed. HsO" " ions do not react with any of the natural components of air, as these have proton affinities lower than that of H2O molecules this is illustrated in Table 1. This table also shows that common VOCs containing a polar functional group or unsaturated bonds (e.g. alkenes, arenes) have proton affinities larger than that of H2O and therefore proton transfer occurs between H30" and any of these compounds (see Equation 4). The measured thermal rate constants for proton transfer to VOCs are nearly identical to calculated thermal, collisional limiting values (Table 1), illustrating that proton transfer occurs on every collision. 

If the parent level k) = vk, Jp) of the optically pumped molecule has been oriented by polarized light, this orientation is partly transferred by collisions to the levels vk - Av, Jk - AJ). This can be monitored by measuring the polarization ratio 7 p = (7 — 7 l)/(/ + / l) of the collisional satellite lines in the fluorescence [996]. 

Chiral amines have been shown to be able to quench the fluorescence of several fluorophores. The first cases were reported by Irie and coworkers, who described that the collisional quenching of (/ )-binaphthyl by A, A -dimethyl-l-phenylethyl-amine was dependent on the stereochemistry of the latter [50]. The mechanism of this process corresponds to a series of subsequent events formation of an encounter complex between the excited fluorophore and the quencher, which can then give rise to a tight exciplex ([A-F ] in Fig. 2a) or to an electron transfer ion pair [ A -F ] (Fig. 2a). This can explain the strOTig dependence of both quenching and enantios-electivity uprm the polarity of the solvent observed in these studies [126]. 

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