Spectra, atomic fundamental

Whereas the emission spectrum of the hydrogen atom shows only one series, the Balmer series (see Figure 1.1), in the visible region the alkali metals show at least three. The spectra can be excited in a discharge lamp containing a sample of the appropriate metal. One series was called the principal series because it could also be observed in absorption through a column of the vapour. The other two were called sharp and diffuse because of their general appearance. A part of a fourth series, called the fundamental series, can sometimes be observed. 

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. 

In cases where information about atomic arrangements cannot be obtained by X-ray crystallography owing to the insolubility or instability of a compound, vibrational spectroscopy may provide valuable insights. For example, the explosive and insoluble black solid SesNaCla was shown to contain the five-membered cyclic cation [SesNaCl]" by comparing the calculated fundamental vibrations with the experimental IR spectrum. ... 

The number of fundamental vibrational modes of a molecule is equal to the number of degrees of vibrational freedom. For a nonlinear molecule of N atoms, 3N - 6 degrees of vibrational freedom exist. Hence, 3N - 6 fundamental vibrational modes. Six degrees of freedom are subtracted from a nonlinear molecule since (1) three coordinates are required to locate the molecule in space, and (2) an additional three coordinates are required to describe the orientation of the molecule based upon the three coordinates defining the position of the molecule in space. For a linear molecule, 3N - 5 fundamental vibrational modes are possible since only two degrees of rotational freedom exist. Thus, in a total vibrational analysis of a molecule by complementary IR and Raman techniques, 31V - 6 or 3N - 5 vibrational frequencies should be observed. It must be kept in mind that the fundamental modes of vibration of a molecule are described as transitions from one vibration state (energy level) to another (n = 1 in Eq. (2), Fig. 2). Sometimes, additional vibrational frequencies are detected in an IR and/or Raman spectrum. These additional absorption bands are due to forbidden transitions that occur and are described in the section on near-IR theory. Additionally, not all vibrational bands may be observed since some fundamental vibrations may be too weak to observe or give rise to overtone and/or combination bands (discussed later in the chapter). 

The resulting neutral atoms are excited by the thermal energy of the flame which are fairly unstable, and hence instantly emit photons and eventually return to the ground state (i.e., the lower energy state). The resulting emission spectrum caused by the emitted photons and its subsequent measurement forms the fundamental basis of FES. 

It was fairly straightforward to modify Bohr s model to include the idea of energy sublevels for the hydrogen spectrum and for atoms or ions with only one electron. There was a more fundamental problem, however. The model still could not explain the spectra produced by many-electron atoms. Therefore, a simple modification of Bohr s atomic model was not enough. The many-electron problem called for a new model to explain spectra of all types of atoms. However, this was not possible until another important property of matter was discovered. 

Mass spectrometry is a sensitive analytical technique which is able to quantify known analytes and to identify unknown molecules at the picomoles or femto-moles level. A fundamental requirement is that atoms or molecules are ionized and analyzed as gas phase ions which are characterized by their mass (m) and charge (z). A mass spectrometer is an instrument which measures precisely the abundance of molecules which have been converted to ions. In a mass spectrum m/z is used as the dimensionless quantity that is an independent variable. There is still some ambiguity how the x-axis of the mass spectrum should be defined. Mass to charge ratio should not lo longer be used because the quantity measured is not the quotient of the ion s mass to its electric charge. Also, the use of the Thomson unit (Th) is considered obsolete [15, 16]. Typically, a mass spectrometer is formed by the following components (i) a sample introduction device (direct probe inlet, liquid interface), (ii) a source to produce ions, (iii) one or several mass analyzers, (iv) a detector to measure the abundance of ions, (v) a computerized system for data treatment (Fig. 1.1). 

Diamond is crystallized in cubic form (O ) with tetrahedral coordination of C-C bonds around each carbon atom. The mononuclear nature of the diamond crystal lattice combined with its high symmetry determines the simplicity of the vibrational spectrum. Diamond does not have IR active vibrations, while its Raman spectrum is characterized by one fundamental vibration at 1,332 cm . It was found that in kimberlite diamonds of gem quality this Raman band is very strong and narrow, hi defect varieties the spectral position does not change, but the band is slightly broader (Reshetnyak and Ezerskii 1990). 

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