X-ray line spectra

X-ray fluorescence spectrometry (XRF) is a non-destructive method of elemental analysis. XRF is based on the principle that each element emits its own characteristic X-ray line spectrum. When an X-ray beam impinges on a target element, orbital electrons are ejected. The resulting vacancies or holes in the inner shells are filled by outer shell electrons. During this process, energy is released in the form of secondary X-rays known as fluorescence. The energy of the emitted X-ray photon is dependent upon the distribution of electrons in the excited atom. Since every element has a unique electron distribution, every element produces... 

X-ray photons result from electronic transitions between the inner energy levels of atoms. When high-energy electrons are absorbed by matter, an x-ray line spectrum results. The structure depends on the substance and is thus used in x-ray spectroscopy. The line spectrum is always formed in conjunction with a continuous background spectrum. The minimum (cutoff) wavelength Xq corresponds to the maximum x-ray energy, This equals the... 

Measurements of the characteristic X-ray line spectra of a number of elements were first reported by H. G. J. Moseley in 1913. He found that the square root of the frequency of the various X-ray lines exhibited a linear relationship with the atomic number of the element emitting the lines. This fundamental Moseley law shows that each element has a characteristic X-ray spectrum and that the wavelengths vary in a regular fiishion form one element to another. The wavelengths decrease as the atomic numbers of the elements increase. In addition to the spectra of pure elements, Moseley obtained the spectrum of brass, which showed strong Cu and weak Zn X-ray lines this was the first XRF analysis. The use of XRF for routine spectrochemical analysis of materials was not carried out, however, until the introduction of modern X-ray equipment in the late 1940s. 

In an electron-excited X-ray spectrum the discrete X-ray lines are superimposed on a continuous background this is the well-known bremsstrahlung continuum ranging from 0 to the primary energy Eq of the electrons. The reason for this continuum is that because of the fundamental laws of electrodynamics, electrons emit X-rays when they are decelerated in the Coulomb field of an atom. As a result the upper energy limit of X-ray quanta is identical with the primary electron energy. 

There are several considerations that go into selecting an X-ray line to excite XPS spectra. Included are the energy of the X-rays and the width of the line. If the energy is too low, the number of photoelectron lines that will be excited will be too small for general use. If the line width is too large, the resolution in the XPS spectrum will also be too small. Therefore, it is useful to consider the processes involved in X-ray generation. 

To illustrate the concept of fluorescence yield, we turn again to the K spectrum. Assume that an element is irradiated with an x-ray line energetic enough to excite the K spectrum. If the irradiation is continued, a steady state will soon be reached in which the rate at which holes are produced in the K shell (i.e., the rate at which atoms in the K state are produced) is just balanced by the combined rates of the various processes causing such holes to disappear. Let n1, n2,. . . , % be the individual rates rii at which the filling of holes leads to the production of the i lines in the K spectrum. The fluorescence yield, for this simple case is... 

This technique can be applied to samples prepared for study by scanning electron microscopy (SEM). When subject to impact by electrons, atoms emit characteristic X-ray line spectra, which are almost completely independent of the physical or chemical state of the specimen (Reed, 1973). To analyse samples, they are prepared as required for SEM, that is they are mounted on an appropriate holder, sputter coated to provide an electrically conductive surface, generally using gold, and then examined under high vacuum. The electron beam is focussed to impinge upon a selected spot on the surface of the specimen and the resulting X-ray spectrum is analysed. 

The emission spectmm of Co, as recorded with an ideal detector with energy-independent efficiency and constant resolution (line width), is shown in Fig. 3.6b. In addition to the expected three y-lines of Fe at 14.4, 122, and 136 keV, there is also a strong X-ray line at 6.4 keV. This is due to an after-effect of K-capture, arising from electron-hole recombination in the K-shell of the atom. The spontaneous transition of an L-electron filling up the hole in the K-shell yields Fe-X X-radiation. However, in a practical Mossbauer experiment, this and other soft X-rays rarely reach the y-detector because of the strong mass absorption in the Mossbauer sample. On the other hand, the sample itself may also emit substantial X-ray fluorescence (XRF) radiation, resulting from photo absorption of y-rays (not shown here). Another X-ray line is expected to appear in the y-spectrum due to XRF of the carrier material of the source. For rhodium metal, which is commonly used as the source matrix for Co, the corresponding line is found at 22 keV. 

PIXE is a primary analytical technique, like NAA, and permits absolute determinations of concentrations. The basis for quantitative PIXE is, as in all X-ray methods, that there exists a relationship between the net peak area of an X-ray line in the spectrum and the amount of element in the sample. One of two methods can be applied to calibration ... 

Figure 2. a) X-ray absorption spectrum near the Mo K-edge of the Co/Mo = 0.125 unsupported Co-Mo catalyst recorded in situ at room temperature b) normalized Mo EXAFS spectrum c) absolute magnitude of the Fourier transform d) fit of the first shell e) fit of the second shell. The solid line in d) and e) is the filtered EXAFS, and the dashed line is the least squares fit. 

Figure 2 X-ray emission spectrum for "(Bi,Pb)2Sr2Ca2CusO10" showing overlap of Pb and B L lines...

Figure 13.3—X-ray emission spectrum produced by an anticathode (anode), measured with a spectrometer, and schematic of an X-ray tube. The line spectrum can be observed as a superposition on the continuum spectrum. It is the continuum portion of this radiation that is solicited for applications that necessitate a high X-ray penetration power, such as for radiology. For analysis, the line spectrum is preferred. Water cooling is compulsory if the X-ray tube operates at high power (1 -4 kW).

Lines, corresponding to different transitions from initial states with vacancy in the shells with the same n, compose a series of spectra, e.g. K-, L-, M-series etc. Main diagram lines correspond to electric dipole ( 1) transitions between shells with different n. The lines of 2-transitions also belong to diagram lines. Selection rules of 1-radiation as well as the one-particle character of the energy levels of atoms with closed shells and one inner vacancy cause, as a rule, a doublet nature of the spectra, similar to optical spectra of alkaline elements. X-ray spectra are even simpler than optical spectra because their series consist of small numbers of lines, smaller than the number of shells in an atom. The main lines of the X-ray radiation spectrum, corresponding to transitions in inner shells, preserve their character also for the case of an atom with open outer shells, because the outer shells hardly influence the properties of inner shells. 

The presence of an outer open shell in an atom, even if this shell does not participate in the transitions under consideration, influences the X-ray radiation spectrum. Interaction of the vacancy with the open shell, particularly in the final state when the vacancy is not in a deep shell, splits the levels of the core. Depending on level widths and relative strength of various intra-atomic interactions, this multiplet splitting leads to broadening of diagram lines, their asymmetry, the occurrence of satellites, or splitting of the spectrum into large numbers of lines. 

A typical x-ray photoelectron spectrum consists of a plot of the intensity of photoelectrons as a function of electron EB or E A sample is shown in Figure 8 for Ag (21). In this spectrum, discrete photoelectron responses from the core and valence electron eneigy levels of the Ag atoms are observed. These electrons are superimposed on a significant background from the Bremsstrahlung radiation inherent in nonmonochromatic x-ray sources (see below) which produces an increasing number of photoelectrons as EK decreases. Also observed in the spectrum are lines due to x-ray excited Auger electrons. 

Fig. S a Valence band spectra of Gd C82 (grey) and C82 (black) measured with Al Ka x-rays, b Symbols Gd 4f photoemission after subtraction of the empty C82 C 2s/2p spectrum. The vertical lines are individual components of atomic calculations for a 4f> multiplet, and the solid curve is their broadened sum. c Gd-N4>5 x-ray absorption spectrum (Gd 4d-4f excitations) of Gd C82. The complex lineshape comes from the widely spaced multiplet components resulting from the strong Coulomb interaction between the single hole in the 4d shell and the eight electrons present in the 4f shell in the x-ray absorption final state [see Fig. lc]. The arrows represent the two photon energies used for the data shown in panel d. d Resonant photoemission data of the valence band region of Gd C82 recorded off (hv=137 eV) and on (hv=149 eV) the Gd 4d-4f giant resonance...

Fig. 14 Solid lines simulated Sc-L23 x-ray absorption spectra of trivalent Sc ions (d°) with an initial-state admixture of the indicated proportion of a d L configuration in the initial state. For details of the calculations, see Ref. [36], Line+symbols experimental Sc-L2 s x-ray absorption spectrum of Sc3N C8o...

Fig. 12.3. a The time-integrated X-ray emission spectrum of laser-irradiated micron-sized Ar clusters measured at an intensity of 1.3 x 1019W/cm2, a pulse duration of 30fs, and a contrast ratio of C = 5 X 10-6. b Enlarged spectrum of a in the vicinity of the Li-like line structure... 

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