Absorbing transition dipole moments

Linear dichroism data with DNA oriented by an electric field [53, 54] or a linear flow [55, 56], under linearly polarised light, lead to determinations of the angle between the absorbing transition dipole moment of the chromophore in the molecule and the DNA helix axis conclusions concerning intercalation may thus be drawn from this technique. Finally, with chiral compounds, circular dichroism is also an attractive method to determine the enantioselectivity in the binding of the molecule [48, 57,58]. 

Figure B3.5.11 The near-UV absorbance transition dipole moment of the tyrosine side chain. The 1Lb transition is seen to be perpendicular to the axis of rotation of the phenolic ring. Interactions of the transition with the environment, expressed as an enhanced CD band, will be sensitive to rotation of the side chain around this axis.

Another related issue is the computation of the intensities of the peaks in the spectrum. Peak intensities depend on the probability that a particular wavelength photon will be absorbed or Raman-scattered. These probabilities can be computed from the wave function by computing the transition dipole moments. This gives relative peak intensities since the calculation does not include the density of the substance. Some types of transitions turn out to have a zero probability due to the molecules symmetry or the spin of the electrons. This is where spectroscopic selection rules come from. Ah initio methods are the preferred way of computing intensities. Although intensities can be computed using semiempirical methods, they tend to give rather poor accuracy results for many chemical systems. 

The intercept, 1/Po, is called the anisotropy of the molecule and is an indication of the nonrotational depolarization of the molecule. This intrinsic depolarization is due to the segmental motion of the fluorophores within the molecule the depolarization due to energy transfer and the angular difference in transition dipole moments of the absorbing and emitting states. 

IR spectroscopy is a powerful and readily available orientation characterization technique. It offers a high chemical selectivity since most functional groups absorb at distinct wavelengths (typically in the 2.5-25 pm range (4,000 00 cm-1 range)), which often depend on their local environment. IR spectroscopy thus provides qualitative and quantitative information about the chemical nature of a sample, its structure, interactions, etc. The potential of IR spectroscopy for orientation characterization stems from the fact that absorption only occurs if the electric field vector of the incident radiation, E, has a component parallel to the transition dipole moment, M, of the absorbing entity. The absorbance, A, is given... 

IR spectroscopy is not only useful for determining the chemical constitution of polymers. It additionally provides profound information on chain orientation and on the orientation of attached lateral substituents of polymers. In this case, polarized IR radiation is applied which is only absorbed by an IR-active bond if the plane in which the electrical field vector E of the IR beam oscillates is parallel to the transition dipole moment p of the vibration to be excited. If, on the other hand, the transition dipole moment p is perpendicular to the electrical field vector E of the IR beam no absorption is observed. Using this effect, the degree of orientation of a polymer sample (film, fiber) can be estimated by comparing the intensity at maximum /(11) and at minimum I ) absorption, i.e., the dichroic ratio. 

In order to evaluate quantitatively the orientation of vibrational modes from the dichroic ratio in molecular films, we assume a uniaxial distribution of transition dipole moments in respect to the surface normal, (z-axis in Figure 1). This assumption is reasonable for a crystalline-like, regularly ordered monolayer assembly. An alternative, although more complex model is to assume uniaxial symmetry of transition dipole moments about the molecular axis, which itself is tilted (and uniaxially symmetric) with respect to the z-axis. As monolayers become more liquid-like, this may become a progressively more valid model (8,9). We define < > as the angle between the transition dipole moment M and the surface normal (note that 0° electric field of the evenescent wave (2,10), in the ATR experiment are given by equations 3-5 (8). 

Absorption in the ultraviolet (k 100 - 400 nm) and the visible (A. 400 - 800 nm) is primarily the result of transitions in the electronic state of the molecule. In such a process, the transition dipole moment would be proportional the overlap in the densities of the charge distributions between the two electron orbitals involved in a transition. The periodic displacement of electrons from one state to another will cause the charge distribution to be anisotropic, with net negative and positive contributions in certain locations within the molecule. The result is the formation of a dipole moment. Very often, dye molecules that absorb in the visible are dispersed within a sample or attached to the molecules of a sample and are used to monitor its degree of alignment. However, since the relative orientation of such a dye molecule to the molecular axes of the constituent sample molecules is often unknown, the interpretation of these measurements can be difficult. 

This deformation can be followed by UV-vis spectroscopy directly at the air/water interface. Upon compression of the monolayer, the absorbance changes not very much around the point where the first increase in surface pressure is recorded (see Figure 6.17), This is caused by the disappearance of the voids between the domains. Above the kink in the isotherm, howevei the K-n band (-323 nm) decreases while the band at 248 nm increases. This increase is due to the increase in chromophore concentration upon compression of the monolayer. The decrease of the 7t-ic band is caused by a preferential orientation of the chromophorra perpendicular to the surface. Chromophores oriented perpendicularly are not detected because the transition dipole of the n-n band is parallel to the probing light. The band at 248 nm, however is not sensitive to the orientation of the chromophore, because the transition dipole moment has a component perpendicular to the long axis of the molecule (see Figure 6.17). 

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