Lifetime, intrinsic experimental determination

The p-Ps has a shorter lifetime than o-Ps and it annihilates into two photons, while o-Ps annihilates into three photons. The intrinsic lifetime is 0.125 ns and 142 ns for the free p-Ps and o-Ps, respectively. In ordinary molecular media, the electron density is low enough so that Ps can pick off electrons from the media that have anti-parallel spin to that of the positron, and undergo two-photon annihilation. This is called the pick-off annihilation of Ps. The pick-off annihilation of o-Ps not only occurs in the form of two-photon annihilation, it also shortens the o-Ps lifetime from 142 ns (free o-Ps) to a few ns. The pick-off annihilation lifetime of o-Ps in molecular systems is about one order of magnitude greater than in crystalline or metallic media. Experimental determination of o-Ps lifetime is one of the most useful methods for positron and positronium chemistry. This is because o-Ps lifetime contains information about electron density, which governs the basic properties of chemical bonding in molecules. It is also controlled by the physical structure of molecules. 

Initiated by the work of Bunker [323,324], extensive trajectory simulations have been performed to determine whether molecular Hamiltonians exhibit intrinsic RRKM or non-RRKM behavior. Both types have been observed and in Fig. 43 we depict two examples, i.e., classical lifetime distributions for NO2 [271] and O3. While Pd t) for NO2 is well described by a single-exponential function — in contrast to the experimental and quantum mechanical decay curves in Fig. 31 —, the distribution for ozone shows clear deviations from an exponential decay. The classical dynamics of NO2 is chaotic, whereas for O3 the phase space is not completely mixed. This is in accord with the observation that the quantum mechanical wave... 

Ln-L distance, energy transfer occurs as long as the higher vibrational levels of the triplet state are populated, that is the transfer stops when the lowest vibrational level is reached and triplet state phosphorescence takes over. On the other hand, if the Ln-L expansion is small, transfer is feasible as long as the triplet state is populated. If the rate constant of the transfer is large with respect to both radiative and nonradiative deactivation of T, the transfer then becomes very efficient ( jsens 1, eqs. (11)). In order to compare the efficiency of chromophores to sensitize Ln - luminescence, both the overall and intrinsic quantum yields have to be determined experimentally. If general procedures are well known for both solutions (Chauvin et al., 2004) and solid state samples (de Mello et al., 1997), measurement of Q is not always easy in view of the very small absorption coefficients of the f-f transitions. This quantity can in principle be estimated differently, from eq. (7), if the radiative lifetime is known. The latter is related to Einstein s expression for the rate of spontaneous emission A from an initial state I J) characterized by a / quantum number to a final state J ) ... 

A more fundamental situation for which dynamical theories are important is when the activated molecule undergoing unimolecular decomposition has vibrational states with lifetimes longer than the statistical RRKM lifetime of the molecule. This will occur if transitions between two (or more) groups of states are less probable than those leading to products. As a result, the molecule will not have a random lifetime distribution even if its initial internal energy distribution is random. Molecules which behave in this manner are said to be "intrinsically" non-RRKM. Long-lived vibrational states have been detected experimentally in highly excited molecules, and it is of considerable interest to determine what... 

Equation 1.72 above relates the radiative lifetime to the magnetic dipole-allowed transition of Eu(III). It is therefore straightforward to determine experimentally, for this ion, tr and therefore the intrinsic emission efficiency. 

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