Deexcitation

PI, PIS Penning ionization [116, 118] Auger deexcitation of metastable noble-gas atoms 4. ... 

MDS Metastable deexcitation spectroscopy [119] Same as PI Surface valence-electron states... 

Internal -> translational energy transfer Surface deexcitation (phonon, electron)... 

The dynamics of fast processes such as electron and energy transfers and vibrational and electronic deexcitations can be probed by using short-pulsed lasers. The experimental developments that have made possible the direct probing of molecular dissociation steps and other ultrafast processes in real time (in the femtosecond time range) have, in a few cases, been extended to the study of surface phenomena. For instance, two-photon photoemission has been used to study the dynamics of electrons at interfaces [ ]. Vibrational relaxation times have also been measured for a number of modes such as the 0-Fl stretching m silica and the C-0 stretching in carbon monoxide adsorbed on transition metals [ ]. Pump-probe laser experiments such as these are difficult, but the field is still in its infancy, and much is expected in this direction m the near fiitiire. 

Electronic transitions fexcitations or deexcitations) can take place during the course of a chemical reaction and have important consequences for its dynamics. The motion of electrons and nuclei were first analyzed in a quantum mechanical framework by Bom and Oppenheimer [1], who separated the... 

Another consequence of the quantum theory of the atomic and nuclear systems is that no two protons, or two neutrons, can have exactly the same wave function. The practical appHcation of this rule is that only a specific number of particles can occupy any particular atomic or nuclear level. This prevents all of the electrons of the atom, or protons and neutrons in the nucleus, from deexciting to the single lowest state. 

The decay of radioisotopes iavolves both the decay modes of the nucleus and the associated radiations that are emitted from the nucleus. In addition, the resulting excitation of the atomic electrons, the deexcitation of the atom, and the radiations associated with these processes all play a role. Some of the atomic processes, such as the emission of K x-rays, are inherently independent of the nuclear processes that cause them. There are others, such as internal conversion, where the nuclear and atomic processes are closely related. 

The Co nucleus decays with a half-life of 5.27 years by /5 emission to the levels in Ni. These levels then deexcite to the ground state of Ni by the emission of one or more y-rays. The spins and parities of these levels are known from a variety of measurements and require that the two strong y-rays of 1173 and 1332 keV both have E2 character, although the 1173 y could contain some admixture of M3. However, from the theoretical lifetime shown ia Table 7, the E2 contribution is expected to have a much shorter half-life and therefore also to dominate ia this decay. Although the emission probabilities of the strong 1173- and 1332-keV y-rays are so nearly equal that the difference cannot be determined by a direct measurement, from measurements of other parameters of the decay it can be determined that the 1332 is the stronger. Specifically, measurements of the continuous electron spectmm from the j3 -decay have shown that there is a branch of 0.12% to the 1332-keV level. When this, the weak y-rays, the internal conversion, and the internal-pair formation are all taken iato account, the relative emission probabilities of the two strong y-rays can be determined very accurately, as shown ia Table 8. 

AIterna.tives to y-Ray Emission. y-Ray emission results ia the deexcitation of an excited nuclear state to a lower state ia the same nucHde, ie, no change ia Z or. There are two other processes by which this transition can take place without the emission of a y-ray of this energy. These are internal conversion and internal pair formation. The internal-conversion process iavolves the transfer of the energy to an atomic electron. 

Figure 1 Schematic of inner sheil ionization and subsequent deexcitation by the Auger...

In the presence of exciting radiation of constant energy, a steady state is established between the excitation and deexcitation processes. 

When an excited state is converted by ejection of an atomic electron, a high positive charge can be produced through subsequent Auger electron emission. Within the period of molecular vibration this charge is spread throughout the molecule to all atoms, and a Coulomb explosion results. This primary phenomenon occurs, of course, not only as a result of [ decay, but must be taken into account in all cases of nuclear reaction when deexcitation by inner electron conversion occurs... 

The difficulty in proving the exact nature of prethermal reactions is that they occur too fast for standard solid-state chemical methods. One attractive idea was expressed by Harbottle 29), namely that, if a strong isotope effect is shown, very little subsequent chemical influence can have been felt and the observed species must have been formed by prethermal processes. The supposition here is that isotopic differences come only from differences in the nuclear deexcitation pattern (total energy, y-ray cascades, angular... 

Temperature-dependent luminescence measurements in the range from 77 to 300 K show quenching of the peak luminescence by a factor of about 15. Similar behavior is observed in the lifetime quenching [665, 666], As the band gap of the PECVD a-Si H is about 1.6 eV, nonradiative deexcitation of Er may occur at elevated temperatures. The amount of quenching lies in between that of c-Si and LPCVD a-Si H, just like the bandgap. 

The calorimetric method of detecting EEPs is based on measurements of the thermal effect arising on surfaces featuring high efficiency of deexcitation. This technique was used for evaluating 02( A ) [31] of a... 

A third possible channel of S state deexcitation is the S) —> Ti transition -nonradiative intersystem crossing isc. In principle, this process is spin forbidden, however, there are different intra- and intermolecular factors (spin-orbital coupling, heavy atom effect, and some others), which favor this process. With the rates kisc = 107-109 s"1, it can compete with other channels of S) state deactivation. At normal conditions in solutions, the nonradiative deexcitation of the triplet state T , kTm, is predominant over phosphorescence, which is the radiative deactivation of the T state. This transition is also spin-forbidden and its rate, kj, is low. Therefore, normally, phosphorescence is observed at low temperatures or in rigid (polymers, crystals) matrices, and the lifetimes of triplet state xT at such conditions may be quite long, up to a few seconds. Obviously, the phosphorescence spectrum is located at wavelengths longer than the fluorescence spectrum (see the bottom of Fig. 1). 

I decays to the ground state by fluorescence emission with a lifetime of 3.3 ns (see above), then I returns to A in less than a nanosecond, a process that is slightly thermally activated, strongly sensitive to deuteration, and apparently involves several intermediates [118, 132, 144]. Because no production of the B state is observed during I deexcitation and return to A, states I and B must exchange on timescales at least slower than the nanosecond. 

It has been assumed so far that the nuclei configurations are in equilibrium in the excited state during the time that the different deexcitation kinetic pathways are active. This means that before de-excitation from the excited to the ground state takes place, the atomic nuclei have found new steady-state equilibrium positions corresponding to the new electronic state. The electronic transition from the ground state to the excited state happens so fast that the... 

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