Dissociation pumping

This collision-induced dissociation of electronically excited molecules plays an important role in chemical reactions and has therefore been studied for many molecules [1004-1006]. The collision cross sections for this process may be sufficiently large to generate inversion between atomic levels. Laser action based on dissociation pumping has been demonstrated. Examples are the powerful iodine laser [1007] and the Cs laser [1008]. 

Stock C, Li X, Keller H-M, Schinke R and Temps F 1997 Unimolecular dissociation dynamics of highly vibrationally excited DCO x-A t- I- Investigation of dissociative resonance states by stimulated emission pumping spectroscopy J. Cham. Phys. 106 5333-58... 

The dynamics of fast processes such as electron and energy transfers and vibrational and electronic deexcitations can be probed by using short-pulsed lasers. The experimental developments that have made possible the direct probing of molecular dissociation steps and other ultrafast processes in real time (in the femtosecond time range) have, in a few cases, been extended to the study of surface phenomena. For instance, two-photon photoemission has been used to study the dynamics of electrons at interfaces [ ]. Vibrational relaxation times have also been measured for a number of modes such as the 0-Fl stretching m silica and the C-0 stretching in carbon monoxide adsorbed on transition metals [ ]. Pump-probe laser experiments such as these are difficult, but the field is still in its infancy, and much is expected in this direction m the near fiitiire. 

In the semidirect process, (Fig. 23) the taw coke oven gas is cooled to condense tar and ammonia Hquor. The heavy layer, tar phase, is pumped to storage and the aqueous layer containing free and fixed ammonia is subsequendy processed in a stiH operation. Free ammonia is that which is in a form which readily dissociates by heat. Fixed ammonia is in a form which requites the presence of an alkaH, such as milk of lime, to effect the ammonia release. 

A dilute I2/CCI4 solution was pumped by a 520 nm visible laser pulse, promoting the iodine molecule from its ground electronic state X to the excited states A,A, B, and ti (Fig. 4). The laser-excited I2 dissociates rapidly into an unstable intermediate (I2). The latter decomposes, and the two iodine atoms recombine either geminately (a) or nongeminately (b) ... 

Figure 1.3. Real-time femtosecond spectroscopy of molecules can be described in terms of optical transitions excited by ultrafast laser pulses between potential energy curves which indicate how different energy states of a molecule vary with interatomic distances. The example shown here is for the dissociation of iodine bromide (IBr). An initial pump laser excites a vertical transition from the potential curve of the lowest (ground) electronic state Vg to an excited state Vj. The fragmentation of IBr to form I + Br is described by quantum theory in terms of a wavepacket which either oscillates between the extremes of or crosses over onto the steeply repulsive potential V[ leading to dissociation, as indicated by the two arrows. These motions are monitored in the time domain by simultaneous absorption of two probe-pulse photons which, in this case, ionise the dissociating molecule.

Figure 1.4. Experimental and theoretical femtosecond spectroscopy of IBr dissociation. Experimental ionisation signals as a function of pump-probe time delay for different pump wavelengths given in (a) and (b) show how the time required for decay of the initally excited molecule varies dramatically according to the initial vibrational energy that is deposited in the molecule by the pump laser. The calculated ionisation trace shown in (c) mimics the experimental result shown in (b).

For both reactions studied, NO+CO and NO+propene, the effect of electrochemically pumped Na in increasing the extent of NO dissociation is large and significant. This is because unpromoted low index planes of Pt, Pt(lll), are relatively inert towards NO dissociation and we adscribe the NO dissociation as the key reaction-initiating step. Such dissociation of diatomic molecules in the field of coadsorbed cations has been discussed in detail by Lang et al [29], The rates of production of CO2. N2 and NjO all depend on... 

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