Radiative transition definition

Delayed Fluorescence. By definition the fluorescence emissions are spin-allowed radiative transitions of atoms or molecules they have short lifetimes, of the order of ns to a few hundred ns. There are however some cases where molecules emit the very same fluorescence spectra but with much longer decays and often with complex non-exponential kinetics. These... 

On the other hand, most chemists and many physicists leading with polyatomic organic molecules currently employ the mechanistic definitions advanced by G. N. Lewis and shown in Figure 1. Thus, fluorescence is defined as a radiative transition between states of like multiplicity, e.g., 5 x - So + hv. Phosphorescence is a radiative transition between states of different multiplicity. In organic molecules the process is usually associated with spin-forbidden transitions such as Ti - S0 + hv". 

Section BT1.2 provides a brief summary of experimental methods and instmmentation, including definitions of some of the standard measured spectroscopic quantities. Section BT1.3 reviews some of the theory of spectroscopic transitions, especially the relationships between transition moments calculated from wavefiinctions and integrated absorption intensities or radiative rate constants. Because units can be so confusing, numerical factors with their units are included in some of the equations to make them easier to use. Vibrational effects, die Franck-Condon principle and selection mles are also discussed briefly. In the final section, BT1.4. a few applications are mentioned to particular aspects of electronic spectroscopy. 

Confusion reigns when one examines the definitions of fluorescence and phosphorescence in different areas of the literature of the natural sciences. Many physicists in particular prefer the operational definition in which fluorescence is described as short-lived emission and phosphorescence is long-lived emission (4,15). However, the question arises as to what constitutes short-lived. A possible transition point may be radiative lifetimes, r0 (vide infra), of the order of 10-s to 10 6 sec. 

The first electronic transition in butadiene has been the subject of many experimental and theoretical studies.The absorption, which has a maximum at 2100 A., is strong and represents a tt tt transition from a ground singlet to an upper singlet state. Analysis of the spectrum, which shows very little structure, has not been carried out. Since no fluorescent radiation has ever been detected on excitation of any of the simple dienes even at low temperature, a definite assignment of the 0 — 0 band has not been made. The 0 — 0 band had been placed at 2300 A. (124 kcal./mole), at which point the absorption is only /so as intense as at its maximum. The oscillator strength is 0.53, which leads to a radiative lifetime of 10 sec. Since emission of radiation has not... 

The spectral overlap integral J can be expressed in terms of either wavenumbers or wavelengths (Equation 2.36). The area covered by the emission spectrum of D is normalized by definition and the quantities / and lx are the normalized spectral radiant intensities of the donor D expressed in wavenumbers and wavelengths, respectively. Note that the spectral overlap integrals J defined here differ from those relevant for radiative energy transfer (Equation 2.33). Only the spectral distributions of the emission by D /,P and, are normalized, whereas the transition moment for excitation of A enters explicitly by way of the molar absorption coefficient sA. The integrals J" and Jx are equal, because the emission spectrum of D is normalized to unit area and the absorption coefficients sA are equal on both scales. 

The prospects for actinide lasers, based on available spectroscopic data, is definitely more limited. Although there are a few prospects for visible lasers, the presence of low-lying 6d and electron transfer states can cause intense excited-state absorption, thus limiting oscillation principally to the infrared. Strong ion-host interactions increase the probabilities for radiative and nonradiative transitions and must be carefully considered with respect to the overall operation and efficiency of any practical system. 

The relationships between measurable quantities related to absolute transition probability (e.g. absorption cross section, molar absorption or extinction coefficient, radiative lifetime) and the fundamental quantities used to describe and inter-relate the observable quantities axe fraught with difficulties of unit conversions and internally consistent treatments of initial- and final-state degeneracies. Several excellent papers on this subject exist (Hilborn, 1982 and 2002, Larsson, 1983, Tatum, 1967, Schadee, 1978, and Whiting, et al., 1980). Much of Section 6.1.1 is based on or checked against Hilborn (1982 and 2002), although slightly different notation and definitions are used. 

Fluorescence Resonance Energy Transfer (FRET), Fig. 1 (a) Jablonski diagram illustrating FRET and related processes, including excitation of the donor, radiative (solid line) and non-radiative (dashed lines) relaxation on the donor and acceptor, vibrational relaxation (short curved arrows), and transitions associated with FRET (dotted lines). Processes that determine the FRET efficiency are indicated in bold, (b) Illustration of spectral overlap between Cy3 (donor) emission and Cy5 (acceptor) absorption, (c) Definition of the angles used to calculate... 

For X = K (no subshell) the number of X-ray photons emitted is given by Nk=N(Dk where N is the total number of K holes involved. Here N is equal to the sum of radiative and radiationless transitions. To a first approximation, K radiationless transition probability is nearly independent of Z, while radiative electric-dipole probability is proportional to Z. It justifies useful semiempirical laws based on q)kOcZ /(Z +c), c=constant. They are discussed in [4] which also gives many references on Auger and related processes up to 1971. Due to Coster-Kronig transitions, experimental and theoretical problems are more complicated for X = L, M,. .. Experimental data depend on the primary vacancy distribution which must remain unaltered before the vacancies are filled. Literature provides either total X-shell data(X = L, M,. ..) or partial Xj-subshelldata (Xj = L., Lg, L3,. ..). Definitions... 

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