Cation-electron pairs

Range parameters, b (nm), for the electron—cation pairs formed by high-energy electron radiolysis of hydrocarbon solvents at 300 K... 

Not only has the escape probability of electron—cation pairs in hydrocarbon liquids been widely studied, but also, in semiconductors, the electron—hole pair created by photo-excitation of an electron behaves very similarly and has been similarly analysed [330, 331]. 

Hummel and Luthjens [398] formed electron—cation pairs in cyclohexane by pulse radiolysis. With biphenyl added to the solvent, biphenyl cations and anions were formed rapidly on radiolysis as deduced from the optical spectra of the solutions. The optical absorption of these species decreased approximately as t 1/2 during the 500 ns or so after an 11ns pulse of electrons. The much lower mobility of the molecular biphenyl anion (or cation) than the solvated electron, es, (solvent or cation) increases the timescale over which ion recombination occurs. Reaction of the solvated electron with biphenyl (present in a large excess over the ions) produces a biphenyl anion near to the site of the solvated electron localisation. The biphenyl anion can recombine with the solvent cation or a biphenyl cation. From the relative rates of ion-pair reactions (electron-cation, electron—biphenyl cation, cation—biphenyl anion etc.), Hummel and Luthjens deduced that the cation (or hole) in cyclohexane was more mobile than the solvated electron (cf. Sect. 2.2 [352, 353]). 

The previously discussed characters will influence the electron transfer rates implying anions. One of the simplest examples was given by the rate constant difference observed in reactions in which pyrene (Py) reacts with an electron or an electron-cation pair [44,45]. The same type of difference was measured in the exchange between the radical anion of biphenyl (B) and pyrene (Py) [46]. The reduced reactivity is the consequence of the cation proximity in the ion pair. 

Figure 5. Set of time-resolved UV-near-IR spectroscopic data (3.44-0.99 eV) following the femtosecond UV excitation of an aqueous sodium chloride solution ([H20]/[NaCl] = 55). An instrumental response of the pump-probe configuration at 1.77 eV (n-heptane) is also shown in the middle part of the figure. The ultra-short-lived components discriminated by UV and IR spectroscopy correspond to low or high excited CTTS states (CTTS, CTTS ), electron-atom pairs (Che pairs), and excited hydrated electrons (ehyd )- The spectral signature of relaxed electronic states (ground state of a hydrated electron, (ehyd) electron-cation pairs, a e hyd) observed in the red spectral region.

AD following Hong and Noolandi [325] (see Sect. 2.2). In cyclohexane, the diffusion coefficient of the solvated electron is 10 m s [320]. Ignoring the diffusion of the solvent cation gives an upper bound on this timescale. The range of electron—cation pairs is about 6—7 nm (Table 8) and so the estimate t rl/D 10 s is probably reasonable. This is not inconsistent with the suggestion by Jonah et al. [178] that the scintillator can interfere with the recombination of geminate ion-pairs. 

For a given liquid, the process of photoionization leads to single electron/cation pairs with a range of initial separation distances. A distribution function of separation distances g(r,0,b) may be introduced. The total fraction of ion pairs escaping recombination is then given as... 

Cations at the surface possess Lewis acidity, i.e. they behave as electron acceptors. The oxygen ions behave as proton acceptors and are thus Bronsted bases. This has consequences for adsorption, as we will see. According to Bronsted s concept of basicity, species capable of accepting a proton are called a base, while a Bronsted acid is a proton donor. In Lewis concept, every species that can accept an electron is an acid, while electron donors, such as molecules possessing electron lone pairs, are bases. Hence a Lewis base is in practice equivalent to a Bronsted base. However, the concepts of acidity are markedly different. 

The mere exposure of diphenyl-polyenes (DPP) to medium pore acidic ZSM-5 was found to induce spontaneous ionization with radical cation formation and subsequent charge transfer to stabilize electron-hole pair. Diffuse reflectance UV-visible absorption and EPR spectroscopies provide evidence of the sorption process and point out charge separation with ultra stable electron hole pair formation. The tight fit between DPP and zeolite pore size combined with efficient polarizing effect of proton and aluminium electron trapping sites appear to be the most important factors responsible for the stabilization of charge separated state that hinder efficiently the charge recombination. 

The second spectrum (figure 3b) displays the spectral features of DPP+ radical cation and provides evidence of DPP spontaneous ionization DPB + HZSM-5 -> DPB + HZSM-5 " (eq. 2). The third spectrum (fig. 3c) exhibits a broad band at 425 nm and is assigned to electron-hole pair formation DPB + HZSM-5 " - DPB HZSM-5 + (eq. 3). 

Recombination of DPB+ radical cation can be summarized according to the reactions relating to either direct recombination (DPB+ HZSM-5 - DPB HZSM-5 (Eq. 4)) or to the capture of another electron of the framework by DPB+ (Eq. 3) and electron-hole pair formation as shown above. 

DPB as well as other DPP molecules (t-stilbene, diphenyl-hexatriene) with relatively low ionization potential (7.4-7.8 eV) and low vapor pressure was successfully incorporated in the straight channel of acidic ZSM-5 zeolite. DPP lies in the intersection of straight channel and zigzag channel in the vicinity of proton in close proximity of Al framework atom. The mere exposure of DPP powder to Bronsted acidic ZSM-5 crystallites under dry and inert atmosphere induced a sequence of reactions that takes place during more than 1 year to reach a stable system which is characterized by the molecule in its neutral form adsorbed in the channel zeolite. Spontaneous ionization that is first observed is followed by the radical cation recombination according to two paths. The characterization of this phenomenon shows that the ejected electron is localized near the Al framework atom. The reversibility of the spontaneous ionization is highlighted by the recombination of the radical cation or the electron-hole pair. The availability of the ejected electron shows that ionization does not proceed as a simple oxidation but stands for a real charge separated state. 

This association has its counterpart that was also variously described as an encounter complex, a nonbonded electron donor-acceptor (EDA) complex, a precursor complex, and a contact charge-transfer complex.10 For electrically charged species such as anion/cation pairs (which are relevant to ion-pair annihilation), the pre-equilibrium association results in contact ion pairs (CIP)7 (equation 3)... 

In piperidine the electron lone-pair can occupy either an axial or an equatorial position in 1-methylpiperidine the axial orientation (lb) is favoured by 99 1 over the equatorial (la). PE spectra and ab initio calculations on methylpiperidines indicate that axial 2-methyl substituents lower the amine lone-pair ionization potential by about 0.26 eV, while equatorial 2-methyl substituents as well as methyl groups on carbon atoms 3 and 4 lower the lone-pair IP by less than 0.1 eV63. This establishes the mechanism of stabilization of the amine radical cation as hyperconjugative electron release, which is larger for CC bonds than for CH bonds. The anti-periplanar orientation of the nitrogen lone-pair and the vicinal C—Me bond (lc) is much more favourable for this type of interaction than the synclinal orientation (Id). 

The mechanism for the photoreaction between 133 and cyclohexene can be summarized as in Scheme 8. The initiating electron transfer fluorescence quenching of 133 by cyclohexene resulted in the formation of an w-amino radical-radical cation pair 136. Proton transfer from the 2-position of the cyclohexene radical cation to the nitrogen atom of the a-amino radical leads to another radical cation-radical pair 137. Recombination of 137 at the radical site affords the adduct 134, while nucleophilic attack at the cation radical of 136 leads to another radical pair 138 which is the precursor for the adduct 135. 

Fig. 3-11. Energy for decomposing ionization of compound AB to form gaseous ions A(giD) and via electron-hole pair formation and via cation-anion vacancy pair formation r = reaction coordinate of decomposing ionization e, s semiconductor band gap . vmb) = cation-anion vacancy pair formation energy (Va- Vb-) Lab = decomposing ionization energy of compound AB.

The decomposing ionization will take place preferentially by way ofthe electron-hole pair formation, if the formation energy of the electron-hole pair, e, is smaller than the formation energy of the cation-emion vacancy pair, Hv(ab>, and vice versa. In general, compound semiconductors, in which the band gap is small (e,< Jfv(AB>), will prefer the formation of electron-hole pairs whereas, compound insulators such as sodium chloride, in which the band gap is great (e(>Hv(AB>), will prefer the formation of cation-anion vacancy pairs [Fumi-Tosi, 1964]. 

Returning to ion-pair zirconocene catalysts, the initiation of the polymerisation process requires the displacement of the anion so that the alkene can be coordinated. The mobility of the anion is therefore an important factor and has become the focus of a number of detailed investigations. The original mechanistic scheme of alkene insertion and polymer chain growth (Scheme 8.4) implied dissociation of the anion and formation of a 14-electron cationic intermediate, which then reacted... 

Figure 2 Survival probability of geminate ion pairs as a function of time. The two solid lines correspond to two different values of the initial electron-cation distance. The broken lines show the asymptotic kinetics calculated from Eq. (25). The value of the escape probability for Tq = O.Sr is indicated by

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