Of electromagnetic radiation

As discussed in more detail elsewhere in this encyclopaedia, many optical spectroscopic methods have been developed over the last century for the characterization of bulk materials. In general, optical spectroscopies make use of the interaction of electromagnetic radiation with matter to extract molecular parameters from the substances being studied. The methods employed usually rely on the examination of the radiation absorbed. 

To get the frequency v in centimeters-, the nonstandard notation favored by spectioscopists, one divides the frequency in hertz by the speed of light in a vacuum, c = 2.998 x lO " cm s-, to obtain a reciprocal wavelength, in this case, 4120 cm-. This relationship arises because the speed of any running wave is its frequency times its wavelength, c = vX in the case of electromagnetic radiation. The Raman spectral line for the fundamental vibration of H2 is 4162 cm-. .., not a bad comparison for a simple model. 

The electric field of electromagnetic radiation completes 4.00 x lO - " complete cycles in 1.00 s. What are the period and frequency of the oscillation, and what is its wavelength What is the frequency in units of cm ... 

The hydrogen atom attached to an alkane molecule vibrates along the bond axis at a frequency of about 3000 cm. What wavelength of electromagnetic radiation is resonant with this vibration What is the frequency in hertz What is the force constant of the C II bond if the alkane is taken to be a stationary mass because of its size and the H atom is assumed to execute simple harmonic motion ... 

To see how this result is used, consider the integral that arises in formulating the interaction of electromagnetic radiation with a molecule within the electric-dipole approximation ... 

As diverse as these techniques are all of them are based on the absorption of energy by a molecule and all measure how a molecule responds to that absorption In describing these techniques our emphasis will be on then application to structure determination We 11 start with a brief discussion of electromagnetic radiation which is the source of the energy that a molecule absorbs m NMR IR and UV VIS spectroscopy... 

Structure determination m modern day organic chemistry relies heavily on instrumental methods Several of the most widely used ones depend on the absorption of electromagnetic radiation... 

Absorption of electromagnetic radiation causes a molecule to be excited from Its most stable state (the ground state) to a higher energy state (an excited state)... 

Colorimetry, in which a sample absorbs visible light, is one example of a spectroscopic method of analysis. At the end of the nineteenth century, spectroscopy was limited to the absorption, emission, and scattering of visible, ultraviolet, and infrared electromagnetic radiation. During the twentieth century, spectroscopy has been extended to include other forms of electromagnetic radiation (photon spectroscopy), such as X-rays, microwaves, and radio waves, as well as energetic particles (particle spectroscopy), such as electrons and ions. ... 

The focus of this chapter is photon spectroscopy, using ultraviolet, visible, and infrared radiation. Because these techniques use a common set of optical devices for dispersing and focusing the radiation, they often are identified as optical spectroscopies. For convenience we will usually use the simpler term spectroscopy in place of photon spectroscopy or optical spectroscopy however, it should be understood that we are considering only a limited part of a much broader area of analytical methods. Before we examine specific spectroscopic methods, however, we first review the properties of electromagnetic radiation. 

The interaction of electromagnetic radiation with matter can be explained using either the electric field or the magnetic field. For this reason, only the electric field component is shown in Figure 10.2. The oscillating electric field is described by a sine wave of the form... 

Thus, for electromagnetic radiation of frequency, V, the wavelength in vacuum is longer than in other media. Another unit used to describe the wave properties of electromagnetic radiation is the wavenumber, V, which is the reciprocal of wavelength... 

Two additional wave properties are power, P, and intensity, I, which give the flux of energy from a source of electromagnetic radiation. 

The division of electromagnetic radiation on the basis of a photon s energy. 

The energy of a photon provides an additional characteristic property of electromagnetic radiation. 

In the previous section we defined several characteristic properties of electromagnetic radiation, including its energy, velocity, amplitude, frequency, phase angle, polarization, and direction of propagation. Spectroscopy is possible only if the photon s interaction with the sample leads to a change in one or more of these characteristic properties. 

A graph of a sample s absorbance of electromagnetic radiation versus wavelength (or frequency or wavenumber). 

In absorption spectroscopy a beam of electromagnetic radiation passes through a sample. Much of the radiation is transmitted without a loss in intensity. At selected frequencies, however, the radiation s intensity is attenuated. This process of attenuation is called absorption. Two general requirements must be met if an analyte is to absorb electromagnetic radiation. The first requirement is that there must be a mechanism by which the radiation s electric field or magnetic field interacts with the analyte. For ultraviolet and visible radiation, this interaction involves the electronic energy of valence electrons. A chemical bond s vibrational energy is altered by the absorbance of infrared radiation. A more detailed treatment of this interaction, and its importance in deter-... 

Absorption of a photon is accompanied by the excitation of an electron from a lower-energy atomic orbital to an orbital of higher energy. Not all possible transitions between atomic orbitals are allowed. For sodium the only allowed transitions are those in which there is a change of +1 in the orbital quantum number ) thus transitions from s—orbitals are allowed, but transitions from s d orbitals are forbidden. The wavelengths of electromagnetic radiation that must be absorbed to cause several allowed transitions are shown in Figure 10.18. 

The attenuation of electromagnetic radiation as it passes through a sample is described quantitatively by two separate, but related terms transmittance and absorbance. Transmittance is defined as the ratio of the electromagnetic radiation s power exiting the sample, to that incident on the sample from the source, Pq, (Figure 10.20a). 

Multiplying the transmittance by 100 gives the percent transmittance (%T), which varies between 100% (no absorption) and 0% (complete absorption). All methods of detection, whether the human eye or a modern photoelectric transducer, measure the transmittance of electromagnetic radiation. 

---