Perturbed intensities

Energies (with isotope perturbation), intensities and polarizations... 

Vibrational spectroscopy (Raman and IR) Energies (with isotope perturbation), intensities and polarisations Identification of ligands coordinated to a metal centre... 

The discussion in Section 6.2.1 was based on the assumption of either r = oo or Tjo = 0. When two interacting basis functions have comparable transition probabilities to a common level, 1% I20, then the perturbed intensities, J+0 and / 0, exhibit a form of anomalous behavior that is explicable as a quantum-mechanical interference effect. 

NMR spectra of samples in which free radical reactions are taking place may show strongly perturbed intensities for lines belonging to reaction products. This effect is called chemically induced dynamic nuclear polarization or CIDNP. Over the past ten years CIDNP has become an established method for mechanistic investigations of reactions involving short-lived radical intermediates. Several reviews and a mono-... 

Nomially the amplitude of the total incident field (or intensity of the incident light) is such that the light/matter coupling energies are sufficiently weak not to compete seriously with the dark matter Hamiltonian. As already noted, when this is tire case, tlie induced polarization, P is treated perturbatively in orders of the total electric field. Thus one writes... 

Most molecular vibrations are well described as hannonic oscillators with small anlrannonic perturbations [5]. Por an hannonic oscillator, all single-quantum transitions have the same frequency, and the intensity of single-quantum transitions increases linearly with quantum number v. Por the usual anhannonic oscillator, the single-quantum transition frequency decreases as v increases. Ultrashort pulses have a non-negligible frequency bandwidth. Por a 1... 

These so-called interaction perturbations Hint are what induces transitions among the various electronic/vibrational/rotational states of a molecule. The one-electron additive nature of Hint plays an important role in determining the kind of transitions that Hint can induce. For example, it causes the most intense electronic transitions to involve excitation of a single electron from one orbital to another (recall the Slater-Condon rules). 

Here, Ri f and Rf i are the rates (per moleeule) of transitions for the i ==> f and f ==> i transitions respeetively. As noted above, these rates are proportional to the intensity of the light souree (i.e., the photon intensity) at the resonant frequeney and to the square of a matrix element eonneeting the respeetive states. This matrix element square is oti fp in the former ease and otf ip in the latter. Beeause the perturbation operator whose matrix elements are ai f and af i is Hermitian (this is true through all orders of perturbation theory and for all terms in the long-wavelength expansion), these two quantities are eomplex eonjugates of one another, and, henee ai fp = af ip, from whieh it follows that Ri f = Rf i. This means that the state-to-state absorption and stimulated emission rate eoeffieients (i.e., the rate per moleeule undergoing the transition) are identieal. This result is referred to as the prineiple of microscopic reversibility. 

Clearly, Bi f embodies the final-level degeneraey faetor gf, the perturbation matrix elements, and the 2n faetor in the earlier expression for Ri f. The spontaneous rate of transition from the exeited to the lower level is found to be independent of photon intensity, beeause it deals with a proeess that does not require eollision with a photon to oeeur, and is usually denoted Ai f. The rate of photon-stimulated upward transitions from state f to state i (gi Rf i = gi Ri f in the present ease) is also proportional to g(cOf,i), so it is written by eonvention as ... 

Any perturbation from ideal space-group symmetry in a crystal will give rise to diffuse scattering. The X-ray diffuse scattering intensity at some point (hkl) in reciprocal space can be written as... 

As mentioned above, the interpretation of CL cannot be unified under a simple law, and one of the fundamental difficulties involved in luminescence analysis is the lack of information on the competing nonradiative processes present in the material. In addition, the influence of defects, the surface, and various external perturbations (such as temperature, electric field, and stress) have to be taken into account in quantitative CL analysis. All these make the quantification of CL intensities difficult. Correlations between dopant concentrations and such band-shape parameters as the peak energy and the half-width of the CL emission currently are more reliable as means for the quantitative analysis of the carrier concentration. 

The experimental principle is illustrated in Fig. 3. The interaction of the polymer with the liposomal membranes causes the perturbation of the bilayer. This perturbation follows the leakage of calcein from the liposome. Calcein in high concentration in the liposome is self-quenched, but has strong fluorescence intensity by the leak from the liposome. Therefore, the extent of the membrane interaction can be estimated quantitatively from the fluorescence spectroscopy. 

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