Para spin positronium

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... 

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. 

A positron in an electronic media can pick up an electron and form a neutral atom called Positronium (Ps) [9], The existence of Ps and its chemical reaction with molecules was detected from annihilation photons in 1951 [10], Ps is formed in most molecular systems. Due to the different combinations of positron and electron, there are two states of Ps the para-Ps (p-Ps) from the anti-parallel spin, and the ortho-Ps (o-Ps) from the parallel spin combination. The lifetime and the annihilation events for p-Ps and o-Ps are very different from each other, as given by electromagnetic theory. Figure 1.1 shows basic physical properties of Ps and compares them with the H atom, although it should not be considered an isotope of H (see problems 1.5 and 1.6 and answers at the end of this chapter). 

Positrons emitted for a radioactive source (such as 22Na) into a polymeric matrix become thermalized and may annihilate with electrons or form positronium (Ps) (a bound state of an electron and positron). The detailed mechanism and models for the formation of positronium in molecular media can be found in Chapters 4 and 5 of this book. The para-positronium (p-Ps), where the positron and electron have opposite spin, decays quickly via self-annihilation. The long-lived ortho positronium (o-Ps), where the positron and electron have parallel spin, undergo so called pick-off annihilation during collisions with molecules. The o-Ps formed in the matrix is localized in the free volume holes within the polymer. Evidence for the localization of o-Ps in the free volume holes has been found from temperature, pressure, and crystallinity-dependent properties [12-14]. In a vacuum o-Ps has a lifetime of 142.1 ns. In the polymer matrix this lifetime is reduced to between 2 - 4 ns by the so-called pick-off annihilation with electrons from the surrounding molecule. The observed lifetime of the o-Ps (zj) depends on the reciprocal of the integral of the positron (p+(rj) and electron (p.(r)) densities at the region where the annihilation takes place ... 

Positroniums (Ps) have two spin states ortho (o-Ps) (triplet) and para (p-Ps) (singlet). In condensed matter 75% of the Ps formed will be o-Ps and 25% p-Ps and their existence will depend on the existence of regions with low electron density [4]. The lifetime of positrons depends on the overlap integral of the wave functions of the positron and local electrons and, thus, it is related with the electronic structure of the material [5]. Since the positrons thermalize after a few ps, and the subsequent lifetime is roughly two orders of magnitude higher than the thermalization time, the lifetime of positrons within the matter will effectively depend upon the local electron density [5]. Thus, PALS implies the measurement of the lifetime, t, which is the inverse of the annihilation rate, X, defined by [ 1 ] C p r)p r)dr (1)... 

The spin value of both the electron and the positron is 1/2. (The absolute value of the magnetic moment of the positron agrees with that of the electron, i.e., 1 Bohr magneton, but its sign is positive and hence its direction is parallel with the spin.) Accordingly, depending on whether the spins of the electron and the positron in the positronium display antiparallel or parallel orientations, the resultant spin value of the Ps may be 0 or 1 (h/27r). The name of the former is singlet or para-Ps ( Sq. Ps), and that of the latter is triplet or ortho-Ps ( Sji Ps). The former decomposes by 2y- and the latter by 3y-annihilation. 

Another important type of positronium interactions is ortho-para conversion. This can take place if the medium includes paramagnetic species containing unpaired electrons. On collision with such a species, the direction of one of the parallel spins in the orrfco-positronium is reversed, and at the same time the direction of the spin of the unpaired electron in the colliding molecule also reverses. In accordance with its lifetime, the resulting para-positroniunr is then rapidly annihilated. Hence, this effect also leads to a decrease in the lifetime of the positronium. 

Reaction of a positron with an electron gives a metastable positronium (Ps) particle, which may have antiparallel spins (para-positronium, p-Ps) or parallel spins (ort/jo-positronium, o-Ps). Within a polymer, the longer lifetimes of o-Ps may be related to the size, concentration and distribution of free volume elements. There have been a number of studies of PIM-1 by positron annihilation lifetime spectroscopy (PALS) [33-36]. 

A certain fraction of these positrons, however, may enter the bound state of the positronium (Ps), by combining with an electron. Ps can be formed in two ground states either in the triplet or ortho state, with parallel spin orientation and an intrinsic average annihilation lifetime of 1.4 x 10" s, or in the singlet or para state with antiparallel spin orientation, which has an intrinsic average lifetime of 1.25 x 10"l s (Fig. 3). 

In the case of positronium atoms the spin plays a more significant role and distinguishes ground states much more significantly. Determined hy the relative orientation of the spins of the constructing electron and positron, the spin of a Ps atom is either 0 or 1 i. The former is called singlet or para-Ps Ps), while the latter is the triplet or ortho-Ps ( Si, Ps). According... 

Another important interaction of positronium is the ortho-para conversion. It occurs when the substance contains paramagnetic particles with unpaired electrons. When colliding with such a particle, the orientation of one of the parallel spins of ortho-positronium may be reversed, simultaneously with the reversion of the spin of the unpaired electron of the colliding molecule. This interaction takes place via electron exchange between the molecule and o-Ps. The pflra-positronium formed by this process annihilates very rapidly, according to its short mean lifetime. Consequently, this effect also leads to the decrease of the lifetime of positronium. Ortho-para conversion can be demonstrated by the following reaction scheme (vertical arrows show the directions of the spins) ... 

Figure 23 Spin orientation for ortho- and para-positronium.

Positron Annihilation Spectroscopy (PALS) can investigate the free volume existing between polymer chains. The lifetime of particles (positrons) injected into a sample can thus provide information on the void structure existing in polymers and polymer blends. For immiscible polymers, free volume existing at the interface due to poor adhesion can be detected by PALS. In miscible polymers, densification due to favorable interactions may be capable of determination. This technique involves the injection of positrons into a polymeric system from a radioisotope capable of emitting positrons, such as Na. The positrons (positively charged electrons) combine with electrons to annihilate or to form a bound state called a positronium (Ps). If the spins of the positron and electron are antiparaUel, para-positroniums (pPS) with a lifetime of 0.125 ns are formed. If the spins of the positron and electrons are parallel, an orthopositronium (oPs) is formed with a lifetime of 1-5 ns. The oPs hfetime, Ts, is related to the free volume cavity in which the oPs is formed [388,389]. 

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