Infrared radiation, interaction with molecules

In addition to describing the conformation of the hydrocarbon chains for amphiphilic molecules at the A/W interface, external reflectance infrared spectroscopy is also capable of describing the orientation of the acyl chains in these monolayers as a function of the monolayer surface pressure. The analysis of the orientation distribution for an infrared dipole moment at the A/W interface proceeds based on classical electromagnetic theory of stratified layers (2). In particular, when parallel polarized radiation interacts with the A/W interface, the resultant standing electric field has contributions from both the z component of the p-polarized radiation normal to the interface, as well as the x component of the p-polarized radiation in the plane of the interface. The E field distribution for these two... 

Today, organic chemists rely on an array of very powerful instruments that enable them to identify compounds in much less time. With use of these instruments, it is often possible to determine the structure of an unknown compound in less than an hour. Three of the most powerful techniques are presented in this and the following chapters. They are infrared spectroscopy and two related techniques proton and carbon-13 nuclear magnetic resonance spectroscopy. Spectroscopy is the study of the interaction of electromagnetic radiation (light) with molecules. 

When infrared light interacts with the fluctuating electric dipole caused by the vibration of the constituent atoms in molecules or crystals, absorption may occur when the energy of the radiation matches that of the vibration. This fluctuating electric dipole can be considered to arise if two centers (atoms) of equal and opposite charge ( Q) are separated by a distance r, when the dipole moment ( x) will be ... 

Diffuse reflectance or DRIFTS (diffuse reflectance infrared Fourier-lransform spectroscopy) allows the sain)le to be analysed neat, ot diluted in a non-absorbing matrix (e.g. KCl or KBr at 1-5% w/w analyte). DRIFTS also may be used to obtain the spectrum of a solute in a volatile solvent by evaporating the solution onto KBr. When the IR radiation interacts with the powdered sample it will be absorbed, reflected and diffracted. The radiation which has been diffusely reflected contains vibrational information on the molecule. This technique allows non-destructive testing of neat materials and is suited to quantitative analysis, although care must be taken to ensure that a consistent particle size is used. 

Up to this point, the wavefunctions considered do not evolve with time. In some cases, the Hamiltonian may have time-dqtendent terms indicating that the system changes with time. An important example is when electromagnetic radiation interacts with a system. Electromagnetic radiation consists of electric and magnetic fields that oscillate in space and time. When electromagnetic radiation interacts with a molecule (such as in spectroscopy), the oscillating fields will result in a time-dependent element in the complete Hamiltonian for the molecule. As already observed in the case of infrared spectroscopy, this interaction may result in a transition of states. 

As the isoquinoline molecule reorients in the order listed above, the absorption of infrared radiation by the in-plane vibrational modes would be expected to increase, while that of the out-of-plane modes would be predicted to decrease (in accordance with the surface selection rule as described above). In the flat orientation there is no component of the dipole moment perpendicular to the surface for the in-plane modes, and under the surface selection rule these modes will not be able to absorb any of the incident radiation. However, as mentioned above, infrared active modes (and in some cases infrared forbidden transitions) can still be observed due to field-induced vibronic coupled infrared absorption (16-20). We have determined that this type of interaction is present in this particular system. 

In order for the electrical component in electromagnetic radiation to interact with a bond, the bond must have a dipole. Thus symmetrical bonds such as those in O2 or Nj do not absorb infrared radiation. However, the majority of organic molecules have plenty of asymmetry. In even small organic molecules the modes of vibration are complex. This is illustrated by the vibrational modes which can occur in a... 

When exposed to electromagnetic radiation of the appropriate energy, typically in the infrared, a molecule can interact with the radiation and absorb it, exciting the molecule into the next higher vibrational energy level. For the ideal harmonic oscillator, the selection rules are Av = +1 that is, the vibrational energy can only change by one quantum at a time. However, for anharmonic oscillators, weaker overtone transitions due to Av = +2, + 3, etc. may also be observed because of their nonideal behavior. For polyatomic molecules with more than one fundamental vibration, e.g., as seen in Fig. 3.1a for the water molecule, both overtones and... 

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