Atomic level excitation

Historically, EELS is one of the oldest spectroscopic techniques based ancillary to the transmission electron microscope. In the early 1940s the principle of atomic level excitation for light element detection capability was demonstrated by using EELS to measure C, N, and O. Unfortunately, at that time the instruments were limited by detection capabilities (film) and extremely poor vacuum levels, which caused severe contamination of the specimens. Twenty-five years later the experimental technique was revived with the advent of modern instrumentation. The basis for quantification and its development as an analytical tool followed in the mid 1970s. Recent reviews can be found in the works by Joy, Maher and Silcox " Colliex and the excellent books by Raether and Egerton. ... 

The technique of INS is probably the least used of those described here, because of experimental difficulties, but it is also one of the physically most interesting. Ions of He" of a chosen low energy in the range 5-10 eV approach a metal surface and within an interaction distance of a fraction of a nanometer form ion-atom pairs with the nearest surface atoms. The excited quasi molecule so formed can de-excite by Auger neutralization. If unfilled levels in the ion fall outside the range of filled levels of the solid, as for He", an Auger process can occur in which an electron from the va-... 

The following properties are observed for an unknown element. Identify the element from its properties, (a) The neutral atom has two unpaired electrons, (b) One of the valence electrons in the ground state atom has mt = 4 I. (c) The most common oxidation state is +4. (d) If an electron in a hydrogen atom were excited to the same principal quantum level, n, as the valence electrons in an atom of this element, and fell to the n — 1 quantum level, the photon emitted would have an energy of 4.9 X 10—20 J. 

Consider continuous radiation with specific intensity I incident normally on a uniform slab with a source function 5 = Bv(Tex) unit volume per unit solid angle to the volume absorption coefficient Kp and is equal to the Planck function Bv of an excitation temperature Tcx obtained by force-fitting the ratio of upper to lower state atomic level populations to the Boltzmann formula, Eq. (3.4). For the interstellar medium at optical and UV wavelengths, effectively S = 0. 

The existence of outsized hydrogen atoms was inferred early on from the observation that 33 terms of the Balmer series could be observed in stellar spectra, compared to only 12 in the laboratory [58]. More recently [59] Rydberg atoms have been produced by exciting an atomic beam with laser light. When the outer electron of an atom is excited into a very high energy level, it enters a spatially extended orbital which is far outside the orbitals... 

Table 8.7). Thus, intensity and concentration are directly proportional. However, the intensity of a spectral line is very sensitive to changes in flame temperature because such changes can have a pronounced effect on the small proportion of atoms occupying excited levels compared to those in the ground state (p. 274). Quantitative measurements are made by reference to a previously prepared calibration curve or by the method of standard addition. In either case, the conditions for measurement must be carefully optimized with reference to the choice of emission line, flame temperature, concentration range of samples and linearity of response. Relative precision is of the order of 1-4%. Flame emission measurements are susceptible to interferences from numerous sources which may enhance or depress line intensities. 

AAS measures the discrete radiation absorbed when ground state atoms are excited to higher energy levels by the absorption of a photon of energy. The radiant power of the absorbed radiation is related to the absorption coefficient of the ground state atoms using the... 

In the case of oxalic acid dihydrate the isotope effect has diminished by 7 per cent on lowering the temperature from 293°K to 90°K. At room temperature a certain proportion of the hydrogen or deuterium atoms are excited to the first energy level more than 99 per cent of these are promoted in the temperature range of 90°K to 300°K, so that at 90°K thermal effects will have almost completely disappeared and the isotope effect at 0°K should be substantially the same as at 90°K. The expansion in oxalic acid dihydrate must, therefore, be a Kero point energy phenomenon. The reversal of the expansion to a contraction in ice will be discussed later. 

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