Weak localisation

In the presence of weak disorder, one should consider an additional contribution to the resistivity due to weak localisation resulting from quantum interference effects and/or that due to Coulomb interaction effects. A single-carrier weak localisation effect is produced by constructive quantum interference between elastically back-scattered partial-carrier-waves, while disorder attenuates the screening between charge carriers, thus increasing their Coulomb interaction. So, both effects are enhanced in the presence of weak disorder, or, in other words, by defect scattering. This was previously discussed for the case of carbons and graphites [7]. 

Later on. Song et al. [19] performed a four-point resistivity measurement on a large bundle of CNTs of 60 pm diameter and 350 pm distance between the two voltage probes. They interpreted their resistivity, magnetoresistanee and Hall effect results in terms of semimetallie conduction and 2D weak localisation as for the case of disordered turbostratie graphite. 

Fig. 3. Electrical conductance of an MWCNT as a function of temperature at the indicated magnetic fields. The solid line is a fit to the data (see ref. 10). The dashed line separates the contributions to the magnetoconductance of the Landau levels and the weak localisation [10].

So, despite the very small diameter of the MWCNT with respeet to the de Broglie wavelengths of the charge carriers, the cylindrical structure of the honeycomb lattice gives rise to a 2D electron gas for both weak localisation and UCF effects. Indeed, both the amplitude and the temperature dependence of the conductance fluctuations were found to be consistent with the universal conductance fluctuations models for mesoscopic 2D systems applied to the particular cylindrical structure of MWCNTs [10]. 

As shown above, experiments on individual MWCNTs allowed to illustrate a variety of new electrical properties on these materials, including 2D quantum interference effects due to weak localisation and UCFs. However, owing to the relatively large diameters of the concentric shells, no ID quantum effects have been observed. In addition, experimental results obtained on MWCNTs were found difficult to interpret in a quantitative way due to simultaneous contributions of concentric CNTs with different diameters and chiralities. 

In conclusion, wc have shown the interesting information which one can get from electrical resistivity measurements on SWCNT and MWCNT and the exciting applications which can be derived. MWCNTs behave as an ultimate carbon fibre revealing specific 2D quantum transport features at low temperatures weak localisation and universal conductance fluctuations. SWCNTs behave as pure quantum wires which, if limited in length, reduce to quantum dots. Thus, each type of CNT has its own features which are strongly dependent on the dimensionality of the electronic gas. We have also briefly discussed the very recent experimental results obtained on the thermopower of SWCNT bundles and the effect of intercalation on the electrical resistivity of these systems. 

An > dioxygen complex has been prepared as an intermediate in the auto-oxidation of TP complexes, and E.P.R. evidence for such a species has come from studies of the auto-oxidation of Ti(TPP)F trapped in a matrix of Ti(TPP)0 ), however, in contrast with the T dioxygen complexes of cobalt, the spin density is only weakly localised on the dioxygen, and is quite high on the porphyrin ligand. E.P.R. spectroscopy has also been used to demonstrate an dioxygen species formed during the auto-oxidation of a Ti(III)... 

A metallic state has been observed in high quality samples of doped (CH), PPV, PANI, PPy, PMeT and PEDOT. The experimental evidence indicates the following finite conductivity at mK temperatures, linear temperature dependence of thermoelectric power, linear term in specific heat, temperature independent Pauli susceptibility, quantum corrections (weak localisation and e-e interaction) to MC, metallic reflectance and free carrier absorption in the infrared. 

The Hard-Soft-Add-Base (HSAB) theory was developed by Pearson in 1963. According to this theory, Lewis acids and Lewis bases are divided into two groups on one hand hard acids and bases, which are usually small, weakly polarizable species with highly localised charges, and on the other hand soft acids and bases which are large, polarizable species with delocalised charges. A selection of Lewis acids, ordered according to their hardness in aqueous solution is presented in Table 1.3. 

The relative importance of these functions also depends to a considerable extent on the solution conditions. Under favourable conditions of pH, oxidising power and aggressive anion concentration in the solution, Function 1 is probably effective in preventing film breakdown. Under unfavourable conditions for inhibition, localised breakdown will occur at weak points in the oxide film, and Functions 2 and 3 become important in repairing the oxide film. 

The reduced orbital overlap between the radicals reduces the bandwidth and the electronic structures could be better considered as those of a localised rather than itinerant electron system. This poor overlap results in very small antiferromagnetic interactions being observed, and the compounds behave as nearly perfect Curie-Weiss paramagnets. In the cases when improved lateral interactions between the stacks are achieved by change of the substituents85 the compounds behave as weak ID ferromagnets due to the effective orthogonality of the S C interactions. 

The weak entropy determined at the onset of the fi transition indicates that the low-temperature motions are localised. As the temperature increases along the f3 transition, the entropy increases as well and reaches very high values for the high-temperature part of the transition, indicating that more and more cooperative motions are taking place with increasing temperature. 

Charge transfer transitions are best discussed in the language of MO theory (Section 8.2). An L—> M transition involves the transfer of an electron from a nonbonding or weakly-bonding MO localised mainly on the ligand moieties L , to a vacancy in the partly-filled nd subsheli of M. Such a transition is likely to appear in the visible or near UV spectrum if the energy separation between the donor and acceptor orbitals is relatively small. This will be the case if ... 

The same group of coordination polymerisations in which alkene undergoes re complex formation with the metal atom includes the copolymerisation of ethylene, a-olefins, cycloolefins and styrene with carbon monoxide in the presence of transition metal-based catalysts [54-58], In this case, however, the carbon monoxide comonomer is complexed with the transition metal via the carbon atom. Coordination bond formation involves the overlapping of the carbon monoxide weakly antibonding and localised mostly at the carbon atom a orbital (electron pair at the carbon atom) with the unoccupied hybridised metal orbitals and the overlapping of the filled metal dz orbitals with the carbon monoxide re -antibonding orbital (re-donor re bond) [59], The carbon monoxide coordination with the transition metal is shown in Figure 2.2. 

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