Molecular beams product detection

A molecular beam scattering experiment usually involves the detection of low signal levels. Thus, one of the most important considerations is whether a sufficient flux of product molecules can be generated to allow a precise measurement of the angular and velocity distributions. The rate of fonnation of product molecules, dAVdt, can be expressed as... 

Figure B2.3.7. Schematic apparatus of crossed molecular beam apparatus with synclirotron photoionization mass spectrometric detection of the products [12], To vary the scattering angle, the beam source assembly is rotated in the plane of the detector. (By pemrission from AIP.)...

Yang X, Lin J, Lee Y T, Blank D A, Suits A G and Wodtke A M 1997 Universal crossed molecular beams apparatus with synchrotron photoionization mass spectrometric product detection Rev. Sc/. Instrum 68 3317-26... 

Molecular beams provide the answer. We first met molecular beams in Box 4.1, where we saw how a velocity selector is constructed. A molecular beam consists of a stream of molecules moving in the same direction with the same speed. A beam may be directed at a gaseous sample or into the path of a second beam, consisting of molecules of a second reactant. The molecules may react when the beams collide the experimenters can then detect the products of the collision and the direction at which the products emerge from the collision. They also use spectroscopic techniques to determine the vibrational and rotational excitation of the products. 

Steady-state molecular beam studies of the reaction of methylacetylene on reduced Ti02 (001) surfaces were undertaken to determine whether this reaction could be performed catalytically under UHV conditions. A representative experiment is presented in Figure 1. Prior to each experiment, the surface was sputtered and annealed to a temperature between 400 K and 550 K surfaces prepared in this manner have the highest fraction of Ti(+2) sites (ca. 30% of all surface cations) of any surface we have been able to create by initial sputtering [3]. Thus these are the surfaces most active for cyclotrimerization in TPD experiments [1]. Steady-state production of trimethylbenzene (as indicated by the m/e 105 signal detected by the mass spectrometer) was characterized by behavior typical of more traditional catalysts a jump in activity upon initial exposure of the crystal to the molecular beam, followed by a decay to a lower, constant level of activity over a longer time scale. Experiments of up to 6 hours in duration showed... 

Although TPD is a versatile and useful technique widely available within the surface-science community, it does have some limitations. For one, because the experiments are carried out under vacuum, they can only probe irreversible reactions no readsorption of the desorbing products is possible. In addition, as the temperature is ramped during detection, the surface temperature and the reaction rates become coupled in a way difficult to separate or control. Of particular importance here is the fact that as the reactions proceed and the products desorb, the surface coverages decrease, so the rates at higher temperatures correspond to the new lower surface concentrations. In order to overcome this problem, isothermal kinetic experiments have been carried out using molecular beams [22,23],... 

H2 molecular beam. The H-atom products were detected by the Rydberg tagging TOF technique using the same scheme described in the last paragraph with a rotatable MCP detector. Figure 4 shows the experimental scheme of the crossed beam setup for the 0(1D) + H2 reactive scattering studies. The scheme used for the H + D2(HD) studies is very similar to that used in the 0(1D) + H2 except that the H-atom beam source is generated from HI photodissociation rather than the 0(1D)-atom beam source from 02 photodissociation. 

CROSSED MOLECULAR BEAM REACTIVE SCATTERING TOWARDS UNIVERSAL PRODUCT DETECTION BY SOFT ELECTRON-IMPACT IONIZATION... 

Undoubtedly, the technique most suited to tackle polyatomic multichannel reactions is the crossed molecular beam (CMB) scattering technique with mass spectrometric detection and time-of-flight (TOF) analysis. This technique, based on universal electron-impact (El) ionization coupled with a quadrupole mass filter for mass selection, has been central in the investigation of the dynamics of bimolecular reactions during the past 35 years.1,9-11 El ionization affords, in principle, a universal detection method for all possible reaction products of even a complex reaction exhibiting multiple reaction pathways. Although the technique is not usually able to provide state-resolved information, especially on a polyatomic... 

In this chapter we have discussed the successful implementation in our laboratory, for the first time, of the soft (i.e. low energy) electron-impact ionization method for product detection in crossed molecular beams reactive scattering experiments with mass spectrometric detection. Analogous to the approach of soft photoionization by tunable VUV synchrotron radiation,... 

In the following, an overview of the experimental approaches is presented, including the production and detection methods of free radicals and the techniques for studying free radical photodissociation in the molecular beam. The photochemistry of the free radical systems investigated recently will then be discussed in detail. 

It is now possible to design the experiments using molecular beams and laser techniques such that the initial vibrational, rotational, translational or electronic states of the reagent are selected or final states of products are specified. In contrast to the measurement of overall rate constants in a bulk kinetics experiment, state-to-state differential and integral cross sections can be measured for different initial states of reactants and final states of products in these sophisticated experiments. Molecular beam studies have become more common, lasers have been used to excite the reagent molecules and it has become possible to detect the product molecules by laser-induced fluorescence . These experimental studies have put forward a dramatic change in experimental study of chemical reactions at the molecular level and has culminated in what is now called state-to-state chemistry. 

The beams of reactant molecules A and B intersect in a small scattering volume V. The product molecule C is collected in the detector. The detector can be rotated around the scattering centre. Various devices may be inserted in the beam path, i.e. between reactants and scattering volume and between scattering volume and product species to measure velocity or other properties. The angular distribution of the scattered product can be measured by rotating the detector in the plane defined by two molecular beams. The mass spectrophotometer can also be set to measure a specific molecular mass so that the individual product molecules are detected. 

A molecular beam of XeFj(gas) and a beam of argon ions were directed at the center of a silicon film which had been deposited on a quartz crystal microbalance. The sensitivity of the microbalance was such that the removal of one monolayer of silicon could be detected. In these experiments, the reaction products [e.g., SiF fgas)] were detected using mass spectrometry the surface concentrations were detected using Auger spectroscopy and the rate that material was being removed from the surface was measured with the microbalance. 

Noxon calculated the rate constant of O( D) quenching by 02 on the basis of unit quantum yield and of the equilibrium concentration of 0( >) atoms. His value of 6 x 10 11 cm3 molec"1 sec-1 agrees well with 7 x 10"11 cm3 molec"1 sec" 1 obtained independently (456), indicating that the assumption of unit quantum yield may be justified. Below 1332 A the production of O( S) is energetically possible. Filseth and Welge (348) have observed an emission at 5577 A due to the transition O( S)- O( D) in the flash photolysis of 02 below 1340 A. The intensity is so weak that Xe has to be added to induce the transition. No quantum yield of O(. S) production has been measured. Recently Stone et al. (937) have measured the llight time ofO atoms produced in the Hash photolysis of the molecular beam of 02 in the vacuum ultraviolet. The O atoms are detected by the chcmiionization reaction with samarium. The technique is similar to the one described in Section II 4.1. 

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