Spectra, atomic sharp

Figure B2.5.12 shows the energy-level scheme of the fine structure and hyperfme structure levels of iodine. The corresponding absorption spectrum shows six sharp hyperfme structure transitions. The experimental resolution is sufficient to detennine the Doppler line shape associated with the velocity distribution of the I atoms produced in the reaction. In this way, one can detennine either the temperature in an oven—as shown in Figure B2.5.12 —or the primary translational energy distribution of I atoms produced in photolysis, equation B2.5.35.

Whereas the emission spectrum of the hydrogen atom shows only one series, the Balmer series (see Figure 1.1), in the visible region the alkali metals show at least three. The spectra can be excited in a discharge lamp containing a sample of the appropriate metal. One series was called the principal series because it could also be observed in absorption through a column of the vapour. The other two were called sharp and diffuse because of their general appearance. A part of a fourth series, called the fundamental series, can sometimes be observed. 

If it is possible to put one layer of metal around a fullerene molecule, it is tempting to look for the completion of additional layers also. In the spectra in Fig. 3, the sharp edges at CgoCa o and C7oCaJ i4 would be likely candidates for signaling the completion of a second layer. As we will see below, there is, in fact, a very reasonable way of constructing such a second layer with precisely the number of metal atoms observed in the spectrum. 

Fig. 1-9. Discover " of the absorption edge. The curve shown is for the experiment of Fig. 1-7 with iron and aluminum as the absorbers and elements of increasing atomic number as samples. In this region of the spectrum, absorption by aluminum increases uniformly with X. Iron shows the sharp drop at its K edge. (After Barkla and Sadler, Phil. Mag. [6], 17, 739.)...

TOF spectra of the H atom products have been measured at 18 laboratory angles (from 117.5° to —50° at about 10° intervals). Figure 19 shows a typical TOF spectrum at the laboratory (LAB) angle of —50° (forward direction). By definition, the forwardness and backwardness of the OH product is defined here relative to the 0(7D) beam direction. The TOF spectrum in Fig. 19 consists of a lot of sharp structures. All these sharp structures clearly correspond to individual rotational states of the OH product, indicating that these TOF spectra have indeed achieved rotational state resolution for the 0(1D)+H2 — OH+H reaction. By converting these TOF spectra from the laboratory (LAB) frame to the center-of-mass (CM) frame... 

The idea of a transition between two energy levels suggests that the transition will occur at only one precise frequency as a sharp spike in the absorption or emission spectrum. This is not the case and, in fact, the transitions have an intrinsic width and shape containing information about the local environment of the atoms. The line profile of an atomic transition has contributions from three effects ... 

A number of other models were considered and tested (for example, direct B—H bonding). The most significant test was the IR vibrational spectrum, where a sharp absorption band at 1875 cm-1 was found, corresponding to the Si—H stretch mode softened by the proximity of the B-atom. Had the hydrogen been bonded to boron, a sharp absorption band at 2560 cm-1 would have been expected. Also, Johnson (1985) showed that deuteration produced the expected isotopic shift. The most definitive and elegant proof of the correctness of the Si-H-B bonding model was provided by Watkins and coworkers (1990), on the basis of a parametric vibrational interaction between the isotopes D and 10B. 

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