Line spectmm

In a laboratory generator, electrons are accelerated by a potential around 30 kV towards a solid target, where they are stopped by impact. The output contains the line spectmm superimposed upon a continuous spectrum. The line, or characteristic spectrum is characteristic of the element and is used in X-ray fluorescent analysis to identity the type and amount of an element present in a sample. The continuous radiation is also called the Bremsstrahlung, from the... 

A simple example of how a filter is used is shown in Fig. 8.16. The solid line spectrum is the output of a Rh tube operated at 20 kV with no filter between the tube and the detector. The Rh L line at 2.69 keV is seen, along with a broad continuum of X-rays from 4 to 19 keV. If the Rh L line gets scattered into the detector, as it can from a crystalhne sample, it can be mistaken for an element in the sample or may overlap another line, causing spectral interference. Placing a cellulose filter over the tube window causes the low energy Rh characteristic line to be absorbed only the continuum radiation reaches the detector, as shown by the dotted line spectmm. 

Bohr s theory explained the experimentally observed line spectmm of hydrogen exactly. The theory was discarded because the calculated properties did not correspond closely to experimental measurements for atoms other than hydrogen. 

Example Estimate the uncertainty in g of a single-line spectmm in solution assuming that the centre can be located to within 0.1 of a line-width of 0.01 mT... 

Think About It Look again at the line spectmm of hydrogen in Figure 6.7 and make sure that your result matches one of them. Note that for an emission, Wj is always greater than rtf, and Equation 6.7 gives a positive result. 

Despite its success in reproducing the hydrogen atom spectmm, the Bolir model of the atom rapidly encountered difficulties. Advances in the resolution obtained in spectroscopic experiments had shown that the spectral features of the hydrogen atom are actually composed of several closely spaced lines these are not accounted for by quantum jumps between Bolir s allowed orbits. However, by modifying the Bolir model to... 

GHz spectral line surveys of tliree regions of the W3 giant molecular cloud complex [21]. From such studies, which reveal dramatic differences in the THz spectmm of various objects, molecular astrophysicists hope to classify the evolutionary state of the cloud, just as optical spectra are used to classify stars. 

Figure Bl.16.15. TREPR spectmm after laser flash photolysis of 0.005 M DMPA (5) in toluene, (a) 0.7 ps, 203 K, RE power 10 mW O, lines CH (8), spacing 22.8 G , benzoyl (6), remaining lines due to (7). (b) 2.54 ps, 298 K, RE power 2 mW to avoid nutations, lines of 7 only. Reprinted from [42].

For complexes such as Ar-H2, Ar-HF and Ar-lTCl, vibrational predissociation is a very slow process and does not cause appreciable broadening of the lines in the infrared spectmm. Indeed, for Ar-ITF, ITuang et al [20] showed that... 

The ubiquitous use of the word Tine to describe an experimentally observed transition goes back to the early days of observations of visible spectra with spectroscopes in which the lines observed in, say, the spectmm of a sodium flame are images, formed at various wavelengths, of the entrance slit. Although, nowadays, observations tend to be in the form of a plot of some measure of the intensity of the transition against wavelength, frequency or wavenumber, we still refer to peaks in such a spectmm as lines. 

If the radiofrequency spectmm is due to emission of radiation between pairs of states - for example nuclear spin states in NMR spectroscopy - the width of a line is a consequence of the lifetime, t, of the upper, emitting state. The lifetime and the energy spread, AE, of the upper state are related through the uncertainty principle (see Equation 1.16) by... 

Examples of prolate near-symmetric rotors are the s-trans and s-cis isomers of crotonic acid, shown in Figure 5.8, the a axis straddling a chain of the heavier atoms in both species. The rotational term values for both isomers are given approximately by Equation (5.37) but, because A and B are different for each of them, their rotational transitions are not quite coincident. Figure 5.9 shows a part of a low-resolution microwave spectmm of crotonic acid in which the weaker series of lines is due to the less abundant s-cis isomer and the stronger series is due to the more abundant s-trans isomer. 

Each vibrational transition observed in the gas phase gives rise to what is called a band in the spectmm. The word line is reserved for describing a transition between rotational levels associated with the two vibrational levels giving rise to the fine stmcture of a band. However, in the solid or liquid phase, where this fine stmcture is not present, each vibrational transition is sometimes referred to as a line rather than a band. 

The example of B5H9 serves to show how the chemical shift may be used as an aid to determining the stmcture of a molecule and, in particular, in deciding between alternative stmctures. There are many examples in the literature of this kind of application which is reminiscent of the way in which the chemical shift in NMR spectroscopy may be employed. However there is one important difference in using the two kinds of chemical shift. In XPS there are no interactions affecting closely spaced lines in the spectmm, however close they may be. Figure 8.15 illustrates this for the C lx lines of thiophene. In NMR spectroscopy the spectmm becomes more complex, due to spin-spin interactions, when chemical shifts are similar. 

Single-Bubble Sonoluminescence. The spectra of MBSL and SBSL are dramatically different. MBSL is generally dominated by atomic and molecular emission lines, but SBSL is an essentially featureless emission that iacreases with decreasiag wavelength. For example, an aqueous solution of NaCl shows evidence of excited states of both OH- and Na ia the MBSL spectmm however, the SBSL spectmm of an identical solution shows no evidence of either of these peaks (30). Similady, the MBSL spectmm falls off at low wavelengths, while the SBSL spectmm continues to rise, at least for bubbles containing most noble gases (38). 

A typical x-ray photoelectron spectmm consists of a plot of the iatensity of photoelectrons as a function of electron E or Ej A sample is shown ia Figure 8 for Ag (21). In this spectmm, discrete photoelectron responses from the cote and valence electron energy levels of the Ag atoms ate observed. These electrons ate superimposed on a significant background from the Bremsstrahlung radiation inherent ia n onm on ochrom a tic x-ray sources (see below) which produces an increa sing number of photoelectrons as decreases. Also observed ia the spectmm ate lines due to x-ray excited Auger electrons. 

The lines of primary interest ia an xps spectmm ate those reflecting photoelectrons from cote electron energy levels of the surface atoms. These ate labeled ia Figure 8 for the Ag 3, 3p, and 3t7 electrons. The sensitivity of xps toward certain elements, and hence the surface sensitivity attainable for these elements, is dependent upon intrinsic properties of the photoelectron lines observed. The parameter governing the relative iatensities of these cote level peaks is the photoionization cross-section, (. This parameter describes the relative efficiency of the photoionization process for each cote electron as a function of element atomic number. Obviously, the photoionization efficiency is not the same for electrons from the same cote level of all elements. This difference results ia variable surface sensitivity for elements even though the same cote level electrons may be monitored. 

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