Optical pumping reactional

We describe beamline ID09B at the European Synchrotron Radiation Facility (ESRF), a laboratory for optical pump and x-ray probe experiments to 100-picosecond resolution. The x-ray source is a narrow-band undulator, which can produce up to 1 x 1010 photons in one pulse. The 3% bandwidth of the undulator is sufficiently monochromatic for most diffraction experiments in liquids. A Ti sapphire femtosecond laser is used for reaction initiation. The laser mns at 896 Hz and the wavelength is tunable between 290-1160 nm. The doubled (400 nm) and tripled wavelength (267 nm) are also available. The x-ray repetition frequency from the synchrotron is reduced to 896 Hz by a chopper. The time delay can be varied from 0 ps to 1 ms, which makes it possible to follow structural processes occurring in a wide range of time scales in one experiment. 

For concrete estimates of the parameters of a reaction (3.1) let us turn to diatomic molecules, such as Na2, K2, Te2, which have been studied most in experiments on optical pumping of molecules via depopulation. A number of data characterizing the states and transitions in these objects under conditions typical for such experiments are given in Table 3.7. These parameters are, to a certain extent, characteristic of diatomic molecules in thermal vapors of the first, sixth and seventh group of the periodic system of elements, such as alkali diatomics, S2, Se2,12, etc. These molecules may... 

The simplest and most straightforward idea for producing collisionally polarized molecules in a thermal cell consists of using collisions with the participation of particles which are polarized in the laboratory frame. It seems that the earliest one was the method based on collisions of atoms which have been optically pumped (optically oriented in their ground state) by the Kastler method see Section 1.1, Fig. 1.1. If the gas constitutes a mixture of a molecular and an atomic component, the conditions being specially created in such a way as to produce such optical orientation of the atoms, we must expect, from considerations of spin conservation in molecular reactions, that polarization of the molecular component must also emerge. 

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... 

Figure 8.3 The optical setup, (a) fluorescence signal detected at distal end of optical fiber (b) use of grating to separate the pumping beam and the fluorescence signal (c) fluorescence signal detected at fi"ont end of the fiber (d) fluorescence signal detected beside the optical fiber reaction region...

Time-resolved resonance Raman spectroscopy of 25 in 50% aqueous CH3CN proved that the final product 26 appears with a rate constant of 2.1 x 109 s 1 following pulsed excitation of 25.207 The appearance of 26 was slightly delayed with respect to the decay of (25), A = 3.0 x 109s, that was determined independently by optical pump probe spectroscopy in the same solvent. The intermediate that is responsible for the delayed appearance of 26, t 0.5 ns, is attributed to the triplet biradical 327.462 It shows weak, but characteristic, absorption bands at 445 and 420 nm, similar to those of the phenoxy radical. ISC is presumably rate limiting for the decay of 327, which cyclizes to the spiro-dienone 28. The intermediate 28 is not detectable its decay must be faster than its rate of formation under the reaction conditions. Decarbonylation of 28 to form p-quinone methide (29) competes with hydrolysis to 26 at low water concentrations. Hydrolysis of 29 then yields p-hydroxybenzyl alcohol (30) as the final product. 

The use of accelerated beams, however, raises the old question in chemical kinetics of the relative efficiencies of vibrational and translational energy in supplying the activation energy of a reaction. While vibrational population inversion in a beam can be achieved in selected cases by optical pumping, any beam method in this area will have to compete with chemical laser techniques. In these the decay of emission from the upper vibrational states is monitored in the presence of a quenching gas (i.e. the reaction partner) in the optical cavity itself. 

Light amplification by stimulated emission of radiation was first demonstrated by Maiman in 1960, the result of a population inversion produced between energy levels of chromium ions in a ruby crystal when irradiated with a xenon flashlamp. Since then population inversions and coherent emission have been generated in literally thousands of substances (neutral and ionized gases, liquids, and solids) using a variety of incoherent excitation techniques (optical pumping, electrical discharges, gas-dynamic flow, electron-beams, chemical reactions, nuclear decay). 

Some lasers are solid, others are liquid or gas devices. Population inversion can be achieved by optical pumping with flashlights or with other lasers. It can also be achieved by such methods as chemical reactions, discharges in gases, and recombination emission in semiconducting materiais... 

Optical pumping with lasers may bring an appreciable fraction of all atoms within the volume of a laser beam passing through a vapor cell into an excited electronic state. This allows the observation of collisions between two excited atoms, which lead to many possible excitation channels where the sum of the excitation energies is accumulated in one of the collision partners. Such energy-pooling processes have been demonstrated for Na + Na, where reactions... 

In the electronic ground states of molecules collision-induced transitions represent, for most experimental situations, the dominant mechanism for the redistribution of energy, because the radiative processes are generally too slow. In cases where a nonequilibrium distribution has been produced (for example, by chemical reactions or by optical pumping), these collisions try to restore thermal equilibrium. The relaxation time of the system is determined by the absolute values of collision cross sections. 

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