Excitation emission intensity

The dependence of the X-ray-excited emission intensities on the amount of doped Eu are shown in Fig. 21.24. The intensity of the phosphors increases with the dopant content up to a maximum (x=0.0S) and then it decreases. 

This surprising substitution effect is more clearly seen in Fig. 3a, which shows an excitation-emission intensity contour plot for compound 2, where a saddle point separates the emission maximum at 360 nm from the short-wavelength features. This explains the two qualitatively different emission characteristics observed for 2 in Fig. 2 for high and low excitation energy. 

A fluorescence or phosphorescence spectrum in which the emission intensity at a fixed wavelength is measured as a function of the wavelength used for excitation. 

Standardizing the Method Equations 10.32 and 10.33 show that the intensity of fluorescent or phosphorescent emission is proportional to the concentration of the photoluminescent species, provided that the absorbance of radiation from the excitation source (A = ebC) is less than approximately 0.01. Quantitative methods are usually standardized using a set of external standards. Calibration curves are linear over as much as four to six orders of magnitude for fluorescence and two to four orders of magnitude for phosphorescence. Calibration curves become nonlinear for high concentrations of the photoluminescent species at which the intensity of emission is given by equation 10.31. Nonlinearity also may be observed at low concentrations due to the presence of fluorescent or phosphorescent contaminants. As discussed earlier, the quantum efficiency for emission is sensitive to temperature and sample matrix, both of which must be controlled if external standards are to be used. In addition, emission intensity depends on the molar absorptivity of the photoluminescent species, which is sensitive to the sample matrix. 

The fluorescent emission for quinine at 450 nm can be induced using an excitation frequency of either 250 nm or 350 nm. The fluorescent quantum efficiency is known to be the same for either excitation wavelength, and the UV absorption spectrum shows that 250 is greater than 350- Nevertheless, fluorescent emission intensity is greater when using 350 nm as the excitation wavelength. Speculate on why this is the case. 

Selectivity The selectivity of molecular fluorescence and phosphorescence is superior to that of absorption spectrophotometry for two reasons first, not every compound that absorbs radiation is fluorescent or phosphorescent, and, second, selectivity between an analyte and an interferant is possible if there is a difference in either their excitation or emission spectra. In molecular luminescence the total emission intensity is a linear sum of that from each fluorescent or phosphorescent species. The analysis of a sample containing n components, therefore, can be accomplished by measuring the total emission intensity at n wavelengths. 

X 10 J/K), and T is the temperature in kelvin. From equation 10.35 we can see that excited states with lower energies have larger populations and, therefore, the most intense emission lines. Furthermore, emission intensity increases with temperature. 

Multielemental Analysis Atomic emission spectroscopy is ideally suited for multi-elemental analysis because all analytes in a sample are excited simultaneously. A scanning monochromator can be programmed to move rapidly to an analyte s desired wavelength, pausing to record its emission intensity before moving to the next analyte s wavelength. Proceeding in this fashion, it is possible to analyze three or four analytes per minute. 

In atomic emission, the decrease in emission intensity when light emitted by excited state atoms in the center of a flame or plasma is absorbed by atoms in the outer portion of the flame. 

Standardizing the Method Equation 10.34 shows that emission intensity is proportional to the population of the excited state, N, from which the emission line originates. If the emission source is in thermal equilibrium, then the excited state population is proportional to the total population of analyte atoms, N, through the Boltzmann distribution (equation 10.35). 

When possible, quantitative analyses are best conducted using external standards. Emission intensity, however, is affected significantly by many parameters, including the temperature of the excitation source and the efficiency of atomization. An increase in temperature of 10 K, for example, results in a 4% change in the fraction of Na atoms present in the 3p excited state. The method of internal standards can be used when variations in source parameters are difficult to control. In this case an internal standard is selected that has an emission line close to that of the analyte to compensate for changes in the temperature of the excitation source. In addition, the internal standard should be subject to the same chemical interferences to compensate for changes in atomization efficiency. To accurately compensate for these errors, the analyte and internal standard emission lines must be monitored simultaneously. The method of standard additions also can be used. 

Sensitivity Sensitivity in flame atomic emission is strongly influenced by the temperature of the excitation source and the composition of the sample matrix. Normally, sensitivity is optimized by aspirating a standard solution and adjusting the flame s composition and the height from which emission is monitored until the emission intensity is maximized. Chemical interferences, when present, decrease the sensitivity of the analysis. With plasma emission, sensitivity is less influenced by the sample matrix. In some cases, for example, a plasma calibration curve prepared using standards in a matrix of distilled water can be used for samples with more complex matrices. 

Fluorometry and Phosphorimetry. Modem spectrofluorometers can record both fluorescence and excitation spectra. Excitation is furnished by a broad-band xenon arc lamp foUowed by a grating monochromator. The selected excitation frequency, is focused on the sample the emission is coUected at usuaUy 90° from the probe beam and passed through a second monochromator to a photomultiplier detector. Scan control of both monochromators yields either the fluorescence spectmm, ie, emission intensity as a function of wavelength X for a fixed X, or the excitation spectmm, ie, emission intensity at a fixed X as a function of X. Fluorescence and phosphorescence can be distinguished from the temporal decay of the emission. 

Figure 5 Calculated (left panel) and measured (right panel) Hel excited pliotoemission intensities for a CusPta layer on a Pt(lOO) surface. The curves are labeled with their emission angles.

Room-temperature fluorescence (RTF) has been used to determine the emission characteristics of a wide variety of materials relative to the wavelengths of selected Fraunhofer lines in support of the Fraunhofer luminescence detector remote-sensing instrument. RTF techniques are now used in the compilation of excitation-emission-matrix (EEM) fluorescence "signatures" of materials. The spectral data are collected with a Perkin-Elraer MPF-44B Fluorescence Spectrometer interfaced to an Apple 11+ personal computer. EEM fluorescence data can be displayed as 3-D perspective plots, contour plots, or "color-contour" images. The integrated intensity for selected Fraunhofer lines can also be directly extracted from the EEM data rather than being collected with a separate procedure. Fluorescence, chemical, and mineralogical data will be statistically analyzed to determine the probable physical and/or chemical causes of the fluorescence. 

In the premixed case and for lean conditions (equivalence ratio less than 1), the volumetric rate of reactants consumption q can be estimated from the light emission intensity I of excited radicals like C or CH [28,33] and OH [34] in the reachon zone. This can be used effectively to measure the volumetric rate of reactants consumption ... 

FIG. 13 Langmuir-Blodgett films of dioctadecyldimethylammonium bromide incorporating 6.0-nm-diameter CdS nanoparticles stabilized by 0.2 mM sodium hexametaphosphate. (a) Absorbance spectra for 2, 3, 4, 5, 6, 7, 8, and 13 layers (bottom to top) the inset shows the linearity of the absorbance at 450 nm versus the number of layers, (b) Fluorescence spectra (excitation wavelength = 400 nm) for 2, 3, 4, 6, 8, 13, and 18 layers (bottom to top) the inset shows the emission intensity at 480 nm versus the number of layers. (Reproduced with permission from Ref. 152. Copyright 1994 American Chemical Society.)... 

Figure 5 shows the dependence of the total emission intensity on the excitation intensity and its spectral width obtained from DCM-encapsulated dendrimers. A nitrogen laser (wavelength of 337 run, pulse duration of 4 ns, and repetition rate of 10 Hz) was used as the excitation source. A cylindrical lens focused the excitation beam onto a stripe 200 pm wide on a quartz cuvette... 

Fig. 5. a Total emission intensity, b Linewidth, both as functions of excitation intensity for DCM/dendrimer solution in cuvette. DCM concentration was 4.0 mmol/1. Inset in a shows plot in logarithmic scale at moderate excitation intensity... 

Also bound to the UV-Vis spectral area is fluorescence spectrometry. It is most important with respect to those fluorescent food colorants that have been incorporated into food. In detail it helps to (1) identify a colorant by the spectral pattern of fluorescence excitation and emission spectra, (2) quantify its concentration by the fluorescence emission intensity, (3) qualify the enviromnent into which the colorant molecule is embedded, and (4) perform structural research on the food matter into which the colorant is incorporated. 

Palladium clusters deposited on amorphous carbon have been studied by XPS and UPS [28] and both techniques show broadening of the d-band peak as cluster size increases. The d-threshold shifts towards Ep as cluster size increases. In UPS studies the d-emission of the single atom has its peak at 3.0 eV below Ep, whereas the d-threshold is 2eV below Ep. Palladium clusters evaporated onto Si02 have been studied by UPS [38]. At large coverages of the Pd metal evaporated (> 10 atoms/cm ), a high emission intensity at Ep excited with photons of 21.2 eV (He(I)) or 40.8 eV (He(II)) as excitation source, is observed. This feature is characteristic in the spectra from bulk Pd samples. At the lowest metal coverage (3 x 10 atoms/cm ),... 

Matsuda and Hata [287] have argued that the species that are detectable using OES only form a very small part (<0.1%) of the total amount of species present in typical silane deposition conditions. From the emission intensities of Si and SiH the number density of these excited states was estimated to be between 10 and 10 cm", on the basis of their optical transition probabilities. These values are much lower than radical densities. lO " cm . Hence, these species are not considered to partake in the deposition. However, a clear correlation between the emission intensity of Si and SiH and the deposition rate has been observed [288]. From this it can be concluded that the emission intensity of Si and SiH is proportional to the concentration of deposition precursors. As the Si and SiH excited species are generated via a one-electron impact process, the deposition precursors are also generated via that process [123]. Hence, for the characterization of deposition, discharge information from OES experiments can be used when these common generation mechanisms exist [286]. 

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