Atomic spectral line

Spectroscopists use an empirical formula (the Rydberg equation) to determine the wavelength of a spectral line. Atomic hydrogen displays several series of lines. 

High-resolution spectroscopy used to observe hyperfme structure in the spectra of atoms or rotational stnicture in electronic spectra of gaseous molecules connnonly must contend with the widths of the spectral lines and how that compares with the separations between lines. Tln-ee contributions to the linewidth will be mentioned here tlie natural line width due to tlie finite lifetime of the excited state, collisional broadening of lines, and the Doppler effect. 

The characteristic lines observed in the absorption (and emission) spectra of nearly isolated atoms and ions due to transitions between quantum levels are extremely sharp. As a result, their wavelengths (photon energies) can be determined with great accuracy. The lines are characteristic of a particular atom or ion and can be used for identification purposes. Molecular spectra, while usually less sharp than atomic spectra, are also relatively sharp. Positions of spectral lines can be determined with sufficient accuracy to verify the electronic structure of the molecules. 

Atoms and ions are excited via collisions, probably mainly with electrons, and then emit light. Most elements with ionization energies less than 8 eV exist mainly as singly charged ions in the plasma. Therefore, spectral lines from ions are most intense for these elements, whereas elements with high ionization energies (such as B, Si, Se and As), as well as the easily ionized alkalis (Li, Na, K, Rb, and Cs), emit most strongly as atoms. 

R. I. Botro. In Developments in Atomic Plasma Spectrochemical Analysis. (R. M. Barnes, ed.) Heyden, Philadelphia, 1981. Describes merhod for correction of overlapping spectral lines when using a polychromaror for ICP-OES. 

Bohr s treatment gave spectacularly good agreement with the observed fact that a hydrogen atom is stable, and also with the values of the spectral lines. This theory gave a single quantum number, n. Bohr s treatment failed miserably when it came to predictions of the intensities of the observed spectral lines, and more to the point, the stability (or otherwise) of a many-electron system such as He. 

Because these photons are produced when an electron moves from one energy level to another, the electronic energy levels in an atom must be quantized, that is, limited to particular values. Moreover, it would seem that by measuring the spectrum of an element it should be possible to unravel its electronic energy levels. This is indeed possible, but it isn t easy. Gaseous atoms typically give off hundreds, even thousands, of spectral lines. 

It would appear that measurement of the integrated absorption coefficient should furnish an ideal method of quantitative analysis. In practice, however, the absolute measurement of the absorption coefficients of atomic spectral lines is extremely difficult. The natural line width of an atomic spectral line is about 10 5 nm, but owing to the influence of Doppler and pressure effects, the line is broadened to about 0.002 nm at flame temperatures of2000-3000 K. To measure the absorption coefficient of a line thus broadened would require a spectrometer with a resolving power of 500000. This difficulty was overcome by Walsh,41 who used a source of sharp emission lines with a much smaller half width than the absorption line, and the radiation frequency of which is centred on the absorption frequency. In this way, the absorption coefficient at the centre of the line, Kmax, may be measured. If the profile of the absorption line is assumed to be due only to Doppler broadening, then there is a relationship between Kmax and N0. Thus the only requirement of the spectrometer is that it shall be capable of isolating the required resonance line from all other lines emitted by the source. 

FIGURE 1.10 (a) The visible spectrum, (b) The complete spectrum of atomic hydrogen. The spectral lines have been assigned to various groups called series, two of which are shown with their names. 

We can begin to understand these perplexing features if we suppose that an electron can exist with only certain energies when it is part of a hydrogen atom, and that a spectral line arises from a transition between two of the allowed... 

The observation of discrete spectral lines suggests that an electron in an atom... 

The existence of photons and the relation between their energy and frequency helps to answer one of the questions posed by the spectrum of atomic hydrogen. At the end of Section 1.3 we started to form the view that a spectral line arises from a transition between two energy levels. Now we can see that if the energy difference is carried away as a photon, then the frequency of an individual line in a spectrum is related to the energy difference between two energy levels involved in the transition (Fig. 1.18) ... 

The Humphreys series is set of spectral lines in the emission spectrum of atomic hydrogen that ends in the fifth excited state. 

If an atom emits a photon of radiation of wavelength 5910 nm, to which spectral line in the Humphreys series does that photon correspond (i.e., the lowest-energy spectral line, the second-lowest-energy spectral line, the third-lowest-energy spectral line, etc.) Justify your answer with a calculation. 

In the spectrum of atomic hydrogen, a violet line is observed at 434 nni. Determine the beginning and ending energy levels of the electron during the emission of energy that leads to this spectral line. 

Balmer series A family of spectral lines (some of which lie in the visible region) in the spectrum of atomic hydrogen. 

Spectral overlap of emission and absorption wavelengths Is a potential cause of Interference In atomic absorption spectrometry (57) Thus, (a) the emission line of Fe at 352.424 nm Is close to the resonance line of N1 at 352.454, (b) the emission line of Sb at 217.023 nm Is close to the resonance line of Pb at 216.999 nm, and (c) the emission line of As at 228.812 nm Is close to the resonance line of Cd at 228.802 (57). To date, these practically coincident spectral lines have not been reported to be of practical Importance as sources of analytical Interference In atomic absorption analyses of biological materials. 

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. 

The study of the hydrogen atom also played an important role in the development of quantum theory. The Lyman, Balmer, and Paschen series of spectral lines observed in incandescent atomic hydrogen were found to obey the empirical equation... 

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