Emission-line spectrum

The emission spectrum from a hollow cathode lamp includes, besides emission lines for the analyte, additional emission lines for impurities present in the metallic cathode and the filler gas. These additional lines serve as a potential source of stray radiation that may lead to an instrumental deviation from Beer s law. Normally the monochromator s slit width is set as wide as possible, improving the throughput of radiation, while being narrow enough to eliminate this source of stray radiation. 

In Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), a gaseous, solid (as fine particles), or liquid (as an aerosol) sample is directed into the center of a gaseous plasma. The sample is vaporized, atomized, and partially ionized in the plasma. Atoms and ions are excited and emit light at characteristic wavelengths in the ultraviolet or visible region of the spectrum. The emission line intensities are proportional to the concentration of each element in the sample. A grating spectrometer is used for either simultaneous or sequential multielement analysis. The concentration of each element is determined from measured intensities via calibration with standards. 

Usually, the ultraviolet and visible regions of the spectrum are recorded. Many of the most intense emission lines lie between 200 nm and 400 nm. Some elements (the halogens, B, C, P, S, Se, As, Sn, N, and O) emit strong lines in the vacuum ultraviolet region (170-200 nm), requiring vacuum or purged spectrometers for optimum detection. 

In contrast to the low-pressure lamps (1—130 Pa) which primarily emit at the resonance line at A = 254nm, high-pressure lamps (lO —10 Pa) also produce numerous bands in the UV and VIS regions (Fig. 16). Table 3 lists the emission lines and the relative spectral energies of the most important mercury lamps (see also [44]). The addition of cadmium to a mercury vapor lamp increases the numbei of emission lines particularly in the visible region of the spectrum [45] so that it i. also possible to work at A = 326, 468, 480, 509 and 644 nm [46]. 

Continnous and line emission spectra. From the top down The continuous visible spectrum the line emission spectra for sodium (Na). hydrogen (H). and mercury (Hg). 

Historically, the visible emission lines shown in Figure 15-3 were the first atomic hydrogen lines discovered. They were found in the spectrum of the sun by W. H. Wollaston in 1802. In 1862, A. J. Angstrom announced that there must be hydrogen in the solar atmosphere. These lines were detected first because of the lesser experimental difficulties in the visible spectral region. They are called the "Balmer series because J. J. Balmer was able to formulate a simple mathematical relation among the frequencies (in It S). The ultraviolet series shown in Figure 15-3 was... 

Fig. 10.1.3 Fluorescence excitation and emission spectra (solid lines) and H2O2-triggered luminescence spectrum (dashed line) of Ophiopsila photoprotein (Shimomura, 1986b, revised). The dotted line indicates the in vivo bioluminescence spectrum of Ophiopsila californica plotted from the data reported by Brehm and Morin (1977).

The potential of a tunable dye laser should not be overlooked. A tunable dye laser, employing an organic dye as lasing material allows one to choose any suitable excitation line within a particular region. This is in contrast to the case of a gas ion laser which has a limited number of emission lines at fixed wavelength. Nevertheless, a tunable dye laser has significant drawbacks such as poor resolution imposed by the dye laser linewidth (1.2 cm-1) and a continuous background spectrum which requires the use of a tunable filter 15-18). 

Schematic representation of an apparatus that measures the emission spectrum of a gaseous element. Emission lines appear bright against a dark background. The spectmm shown is the emission spectrum for hydrogen atoms.

The discovery of two other series of emission lines of hydrogen came later. They are named for their discoverers the Lyman series in the ultraviolet range and Paschen series in the infrared region. Although formulas were devised to calculate the spectral lines, the physics behind the math was not understood until Niels Bohr proposed his quantized atom. Suddenly, the emission spectrum of hydrogen made sense. Each line represented the energy released when an excited electron went from a higher quantum state to a lower one. 

Dip the platinum loop in the solution and stick it in the flame. The result is a bright yellow glow. The color comes from two yellow emission lines that dominate the spectrum of sodium. The emission lines result from electrons dropping from the 3p to the 3s orbital. The two lines are very close to one another. The difference in energy is due to the slightly different energies of the electrons in the 3p orbital because of their spin. 

In an actual Mdssbauer transmission experiment, the radioactive source is periodically moved with controlled velocities, +u toward and —d away from the absorber (cf. Fig. 2.6). The motion modulates the energy of the y-photons arriving at the absorber because of the Doppler effect Ey = Eq + d/c). Alternatively, the sample may be moved with the source remaining fixed. The transmitted y-rays are detected with a y-counter and recorded as a function of the Doppler velocity, which yields the Mdssbauer spectrum, r(u). The amount of resonant nuclear y-absorption is determined by the overlap of the shifted emission line and the absorption line, such that greater overlap yields less transmission maximum resonance occurs at complete overlap of emission and absorption lines. 

In the following, we consider the shape and the width of the Mdssbauer velocity spectrum in more detail. We assume that the source is moving with velocity u, and the emission line is an unsplit Lorentzian according to (2.2) with natural width E. If we denote the total number of y-quanta emitted by the source per time unit toward the detector by Nq, the number N E)AE of recoU-free emitted y-rays with energy y in the range to -f dE is given by ([1] in Chap. 1)... 

Fig. 2.6 Schematic illustration of a Mossbauer transmission experiment in five steps. The Absorption bars indicate the strength of recoilless nuclear resonant absorption as determined by the overlap of emission and absorption lines when the emission line is shifted by Doppler modulation (velocities Uj,. .., 1)5). The transmission spectrum T v) is usually normalized to the transmission T oo) observed for v oo by dividing T(v)IT(oo). Experimental details are found in Chap. 3...

Fig. 2.8 (a) Fractional absorption of a Mossbauer absorption line as function of the effective absorber thickness t. (b) The depth of the spectrum is determined by fs. The width for thin absorbers, t 1, is twice the natural line width F of the separate emission and absorption lines (see (2.30)). AE is the shift of the absorption line relative to the emission line due to chemical influence... 

This phosphor has many emission lines in the blue, green, and red areas of the electromagnetic spectrum screens made from it have a whitish appearance... 

Until very recently, studies of the use of luminescent lanthanide complexes as biological probes concentrated on the use of terbium and europium complexes. These have emission lines in the visible region of the spectrum, and have long-lived (millisecond timescale) metal-centered emission. The first examples to be studied in detail were complexes of the Lehn cryptand (complexes (20) and (26) in Figure 7),48,50,88 whose luminescence properties have also been applied to bioassay (vide infra). In this case, the europium and terbium ions both have two water molecules... 

Eventually, other series of lines were found in other regions of the electromagnetic spectrum. The Lyman series was observed in the ultraviolet region, whereas the Paschen, Brackett, and Pfund series were observed in the infrared region of the spectrum. All of these lines were observed as they were emitted from excited atoms, so together they constitute the emission spectrum or line spectrum of hydrogen atoms. 

The chemically induced dynamic nuclear polarization (DNP) opened perspective to study products formed from free radicals [102], The basis of this study is the difference in NMR spectra of normal molecules and those formed from free radicals and radical pairs. The molecules formed from radicals have an abnormal NMR spectrum with lines of emission and abnormal absorption [102]. DNP spectra help to obtain the following mechanistic information ... 

The spectrum of tin emitted from a triggered spark source in the far UV region (17.5-200 nm) has been analysed26. The emission lines in this region may be useful for development of new analytical methods. 

LINERs are weaker emission-line regions in certain elliptical and early-type spiral galaxies (e.g. M51 and M81) showing relatively strong lines of [O I], [N ii] and [S n], similar to SNR. It is not clear whether they are excited by shocks like SNR or by a very dilute (i.e. low u) non-thermal spectrum. 

Fig. 12.9. Composite spectrum of Lyman-break galaxies showing a combination of interstellar and stellar absorption lines, P Cygni features and nebular emission lines, dominated by Lyman-a. After Shapley et al. (2003).

J. Janssen and N. Lockyer independently discover helium from yellow emission line ( D3 ) in spectrum of prominence seen at eclipse. 

The frequencies of hydrogen emission lines in the infrared region of the spectrum other than the visible region would be predicted by replacing the constant 2 in the Balmer equation by the variable m, where m is an integer smaller than n m = 3,4,... 

---