Transition dipole moment, large

For large interchain separations (8 A < R < 30 A), the LCAO coefficients of a given molecular orbital are localized on a single chain, as intuitively expected. The lowest excited state of these dimers results from a destructive interaction of the two intrachain transition dipole moments, whereas a constructive interaction prevails for the second excited stale. This result is fully consistent with the molcc-... 

The discussion in this chapter is limited to cyanine-like NIR conjugated molecules, and further, is limited to discussing their two-photon absorption spectra with little emphasis on their excited state absorption properties. In principle, if the quantum mechanical states are known, the ultrafast nonlinear refraction may also be determined, but that is outside the scope of this chapter. The extent to which the results discussed here can be transferred to describe the nonlinear optical properties of other classes of molecules is debatable, but there are certain results that are clear. Designing molecules with large transition dipole moments that take advantage of intermediate state resonance and double resonance enhancements are definitely important approaches to obtain large two-photon absorption cross sections. 

In general, only dye molecules with a large electronic transition dipole moment pS, Si] are considered in this account, which means that the S < So transition is of n < n type. 

Consequently, molecules with structures that lead to large transition dipole moments and small transition energies should display large second-order hyperpolarizabilities. Conjugated molecules with delocalized electronic wavefunc-tions enable the electrons to move over considerable distances and therefore show large transition and difference dipole moments. Furthermore, these molecules show low transition energies. 

Figure 4.5. Wave vectors around the center of the excitonic Brillouin zone for which coherent emission [solution of equations 4.10 and 4.25] is possible according to the disorder critical value Ac. We notice that r0 is the imaginary eigenvalue for K = 0 (emission normal to the lattice plane) and that K" and K1 indicate, respectively, components of K parallel and perpendicular to the transition dipole moment, assumed here to lie in the 2D lattice. The various curves for constant disorder parameter Ac determine areas around the Brillouin-zone center with (1) subradiant states (left of the curve) and (2) superradiant states (right of the curve). We indicate with hatching, for a large disorder (A,. r ), a region of grazing emission angles and superradiant states for a particular value of A.

Vibrational spectroscopy has been used in the past as an indicator of protein structural motifs. Most of the work utilized IR spectroscopy (see, for example, Refs. 118-128), but Raman spectroscopy has also been demonstrated to be extremely useful (129,130). Amide modes are vibrational eigenmodes localized on the peptide backbone, whose frequencies and intensities are related to the structure of the protein. The protein secondary structures must be the main factors determining the force fields and hence the spectra of the amide bands. In particular the amide I band (1600-1700 cm-1), which mainly involves the C=0-stretching motion of the peptide backbone, is ideal for infrared spectroscopy since it has an large transition dipole moment and is spectrally isolated... 

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