Absorption Induced Emission

This rule is analogous for any number of photons thus, in a three-photon absorption process the allowed states are the p and f states, which allows even-to-odd or odd-to-even parity. This means that transitions can be divided between states of either the same or different parity corresponding to absorption of either even or odd numbers of photons. Hence the selection rules are the same for one and three photons and for two and four photons, respectively [49]. 

The structure-property relationships are affected by three main structural elements-coordination and hence packing, which determines some of the nonlinear harmonics the degree of conjugation along the backbone and the effects of the substituents-all of which have previously been reported to affect two-photon absorption processes thus it is proposed that the same applies for other higher-order systems. However, it is rare for reports of these high-order multiphoton absorption processes displayed by organic metal complexes to be accompanied with detailed molecular structure to show the correlation between the photoproperties. 

5D4 — 7Fj transitions, the emission intensities were of the same order and thus the antenna sensitization was also comparably efficient. 

Multiphoton absorption induced emission from lanthanides emitting in the visible region is by far most studied with Eu and Tb, which are the most widely used metals as they have favorable emission windows and larger separations of 

The lower energy or emission states of lanthanides such as Nd, Er, and Yb can allow excitation at considerably longer wavelengths such as those used for multiphoton processes. However, most problems encountered with these lanthanides are in the choice of appropriate weakly energy-absorbing sensitizers which are often derived from azide dyes and their derivatives [68, 69]. Advances in molecular engineering suggest that such problems will be overcome. 

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At low pressure, the only interactions of the ion with its surroundings are through the exchange of photons with the surrounding walls. This is described by the three processes of absorption, induced emission, and spontaneous emission (whose rates are related by the Einstein coefficient equations). In the circumstances of interest here, the radiation illuminating the ions is the blackbody spectrum at the temperature of the surrounding walls, whose intensity and spectral distribution are given by the Planck blackbody formula. At ordinary temperatures, this is almost entirely infrared radiation, and near room temperature the most intense radiation is near 1000 cm". ... 

The use of lanthanides are common for optical purposes because of their narrow and sharp bands, and distinguishable long lifetimes, accomparied by low transition probabilities due to the forbidden nature of the transitions [10-13]. Thus chromophoric sensitization of ligand to metal has been subjected to numerous theoretical and experimental investigations [14—16]. However, only limited classes of organic-lanthanide complexes have been developed and shown to display nonlinear processes [17-19]. Common nonlinear processes from lanthanide complexes include harmonic generation, photon up-conversion and multiphoton absorption induced emission. 

Figure 7.9 The solid-state linear emission (a) and multiphoton absorption induced emission/SHG (b) spectra of 4 at room temperature.

From these equations one also finds the rate coefficient matrix for themial radiative transitions including absorption, induced and spontaneous emission in a themial radiation field following Planck s law [35] ... 

The general principle of detection of free radicals is based on the spectroscopy (absorption and emission) and mass spectrometry (ionization) or combination of both. An early review has summarized various techniques to detect small free radicals, particularly diatomic and triatomic species.68 Essentially, the spectroscopy of free radicals provides basic knowledge for the detection of radicals, and the spectroscopy of numerous free radicals has been well characterized (see recent reviews2-4). Two experimental techniques are most popular for spectroscopy studies and thus for detection of radicals laser-induced fluorescence (LIF) and resonance-enhanced multiphoton ionization (REMPI). In the photochemistry studies of free radicals, the intense, tunable and narrow-bandwidth lasers are essential for both the detection (via spectroscopy and photoionization) and the photodissociation of free radicals. 

As for any quantum mechanical system interacting with electromagnetic radiation, a photon can induce either absorption or emission. The experiment detects net absorption, i.e., the difference between the number of photons absorbed and the number emitted. Since absorption is proportional to the number of spins in the lower level and emission is proportional to the number of spins in the upper level, net absorption, i.e., absorption intensity, is proportional to the difference ... 

The wide variety of absorption and emission wavelengths has allowed the use of different coumarin derivatives as FRET pairs [37], Contrary to most fluorophores, coumarin is uncharged which makes it intrinsically membrane-permeant. To induce water solubility polar groups are frequently introduced to the basic structure [35],... 

Optical immunosensors are based on the measurement of the absorption or emission of light induced by the immunoreactants [9], They can also be based on evanescent... 

It is useful to view optical absorption and emission processes in such a system in terms of transitions between distinct vibrational levels of the ground and excited electronic states of a metal atom-rare gas complex or quasi-molecule. Since the vibrational motions of the complex are coupled with the bulk lattice vibrations, a complicated pattern of closely spaced vibrational levels is involved and this results in the appearance of a smooth, structureless absorption profile (25). Thus the homogeneous width of the absorption band arises from a coupling between the electronic states of the metal atom and the host lattice vibrations, which is induced by the differences between the guest-host... 

Let us consider a molecule and two of its energy levels E) and f 2- The Einstein coefficients are defined as follows (Scheme B2.2) Bn is the induced absorption coefficient, B2i is the induced emission coefficient and A21 is the spontaneous emission coefficient. 

Fig. 5.9. Rotational motions inducing depolarization of fluorescence. The absorption and emission transition moments are assumed to be parallel.

When protonation of a probe leads to dramatic effects on the electronic absorption and emission as described above, one can expect that cations other than protons might be capable of inducing similar effects if these ions can be made to bind to the basic atom of the probe molecule. A simple but effective method to do so exists in the formal replacement of the amino substituents ofchromophores by aza crowns. In the resulting chromoionophores the amine nitrogens possess simultaneously an electron-donor... 

Provided that a transition is forbidden by an electric dipole process, it is still possible to observe absorption or emission bands induced by a magnetic dipole transition. In this case, the transition proceeds because of the interaction of the center with the magnetic field of the incident radiation. The interaction Hamiltonian is now written as // = Um B, where is the magnetic dipole moment and B is the magnetic field of the radiation. 

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