Positronium annihilation

The sizes and concentration of the free-volume cells in a polyimide film can be measured by PALS. The positrons injected into polymeric material combine with electrons to form positroniums. The lifetime (nanoseconds) of the trapped positronium in the film is related to the free-volume radius (few angstroms) and the free-volume fraction in the polyimide can be calculated.136 This technique allows a calculation of the dielectric constant in good agreement with the experimental value.137 An interesting correlation was found between the lifetime of the positronium and the diffusion coefficient of gas in polyimide.138,139 High permeabilities are associated with high intensities and long lifetime for positron annihilation. 

Network properties and microscopic structures of various epoxy resins cross-linked by phenolic novolacs were investigated by Suzuki et al.97 Positron annihilation spectroscopy (PAS) was utilized to characterize intermolecular spacing of networks and the results were compared to bulk polymer properties. The lifetimes (t3) and intensities (/3) of the active species (positronium ions) correspond to volume and number of holes which constitute the free volume in the network. Networks cured with flexible epoxies had more holes throughout the temperature range, and the space increased with temperature increases. Glass transition temperatures and thermal expansion coefficients (a) were calculated from plots of t3 versus temperature. The Tgs and thermal expansion coefficients obtained from PAS were lower titan those obtained from thermomechanical analysis. These differences were attributed to micro-Brownian motions determined by PAS versus macroscopic polymer properties determined by thermomechanical analysis. 

PALS is based on the injection of positrons into investigated sample and measurement of their lifetimes before annihilation with the electrons in the sample. After entering the sample, positron thermalizes in very short time, approx. 10"12 s, and in process of diffusion it can either directly annihilate with an electron in the sample or form positronium (para-positronium, p-Ps or orto-positronium, o-Ps, with vacuum lifetimes of 125 ps and 142 ns, respectively) if available space permits. In the porous materials, such as zeolites or their gel precursors, ort/zo-positronium can be localized in the pore and have interactions with the electrons on the pore surface leading to annihilation in two gamma rays in pick-off process, with the lifetime which depends on the pore size. In the simple quantum mechanical model of spherical holes, developed by Tao and Eldrup [18,19], these pick-off lifetimes, up to approx. 10 ns, can be connected with the hole size by the relation ... 

Positron annihilation spectroscopy (PAS) was first applied to investigate [Fe(phen)2(NCS)2] [77]. The most important chemical information provided by the technique relates to the ortho-positronium lifetime as determined by the electron density in the medium. It has been demonstrated that PAS can be used to detect changes in electron density accompanying ST or a thermally induced lattice deformation, which could actually trigger a ST [78]. 

These traps, (Fig. 6) and similar effects in the motion of holes and other charges through polymers, would eventually be correlated also with such structural probes as positron lifetimes in macromolecular solids. Extensive recent studies of positron lifetime are based on positronium decay. In this, the lifetime of o-positronium (bound positron-electron pair with total spin one) is reduced from about 140 nanoseconds to a few nanoseconds by "pick-off annihilation" in which some unpaired electron spins in the medium cause conversion quenching of orthopositronium to para-positronium. The speed of the t2 effect is supposed, among other things, to represent by pick-off annihilation the presence of defects in the crystalline lattice. In any case, what amounts to empty space between molecules can then be occupied by orthopositronium.(14,15,16) It is now found in linear polyethylene, by T. T. Wang and his co-workers of Bell Laboratories(17) that there is marked shift in positron lifetimes over the temperature range of 80°K to 300°K. For... 

Positron annihilation lifetime spectroscopy (PALS) provides a method for studying changes in free volume and defect concentration in polymers and other materials [1,2]. A positron can either annihilate as a free positron with an electron in the material or capture an electron from the material and form a bound state, called a positronium atom. Pnra-positroniums (p-Ps), in which the spins of the positron and the electron are anti-parallel, have a mean lifetime of 0.125 ns. Ortho-positroniums (o-Ps), in which the spins of the two particles are parallel, have a mean lifteime of 142 ns in vacuum. In polymers find other condensed matter, the lifetime of o-Ps is shortened to 1-5 ns because of pick-off of the positron by electrons of antiparallel spin in the surrounding medium. 

This inevitably leads to the annihilation of anti-particles from the bound states of protonium (Pn = pp) and positronium (Ps = e+e ). We found this reaction to be a very important mechanism for the loss of antihydrogen [26, 27, 29]. 

When the two conjugated atoms approach each other, the leptons might in principle annihilate before the hadrons do. We have found that this is not the case. Even though the annihilation reaction constant for para-positronium is larger than that for protonium, the probability of e+ — e annihilation at any given interhadronic distance R is weighted by the hadronic probability density at that distance. Because of that, the e+ — e annihilation occurs mainly at R 1 whereas the hadrons annihilate basically at R = 0. 

Positronium can exist in the two spin states, S = 0, 1. The singlet state (5 = 0), in which the electron and positron spins are antiparallel, is termed para-positronium (para-Ps), whereas the triplet state (5 = 1) is termed ortho-positronium (ortho-Ps). The spin state has a significant influence on the energy level structure of the positronium, and also on its lifetime against self-annihilation. 

The need to conserve angular momentum and to impose CP invariance led Yang (1950) and Wolfenstein and Ravenhall (1952) to conclude that positronium in a state with spin 5 and orbital angular momentum L can only annihilate into n7 gamma-rays, where... 

This selection rule does not appear to exclude radiationless annihilation and annihilation into a single gamma-ray, but these modes of annihilation are nevertheless forbidden for free positronium. 

The lowest order contributions to the annihilation rates for the nPs1So and nPS3Si states of positronium were first calculated by Pirenne (1946)... 

The total positron scattering cross section, erT, is the sum of the partial cross sections for all the scattering channels available to the projectile, which may include elastic scattering, positronium formation, excitation, ionization and positron-electron annihilation. Elastic scattering and annihilation are always possible, but the cross section for the latter process is typically 10-2O-10-22 cm2, so that its contribution to erT is negligible except in the limit of zero positron energy. All these processes are discussed in greater detail in Chapters 3-6. 

Because of its relative simplicity, particular attention has been devoted to positronium formation in positron collisions with atomic hydrogen. Within the Ore gap the two open channels (other than direct annihilation) are... 

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