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Barrier height factors which decrease

For the DTO model we must have an estimate of the torsional vibration frequency and the barrier to internal rotation of the constituent monomers. The DTO model fits the experimental data for bulk polymer if H = 5.4 kcal/mole, vt — 1012 c.p.s., and Zt = 30 which are not unreasonable values. One would expect the barrier height to decrease upon dilution (if it changes at all) as the chain environment loosens up. Assuming that rotation about C—O—C bonds is predominate, we take the experimental values of H = 2.63 kcal/mole, vt = 7.26 x 1012 c.p.s. of Fateley and Miller (14) for dimethyl ether. Eq. (2.8) predicts rSJ° = 0.47 X 10-8 sec at 253° K with Zt = 30. We shall use this as our dilute solution result. [The methyl pendant in polypropylene) oxide will act to increase the barrier height due to steric effects, making this calculated relaxation time somewhat low for this choice of a monomer analog.] Tmax is seen to change only by a factor of 102—103 upon dilution in the DTO model. [Pg.110]

In conclusion, the protein motion that compresses the oxygen stack, is one of the factors which makes the reaction possible, leading up to a 20% decrease in barrier height. [Pg.341]

Typical room temperature current-voltage (Z-V) characteristics of Ni/Au SDs are plotted in Figure 6.13. As we can see, the saturation current decreases monotonously with increasing SiN.r deposition time from 0 (the control sample) to 5 min which means that the effective Schottky barrier height increased owing to shallow defect reduction. Meanwhile, the series resistance and ideality factor also decreased when longer SiN deposition times were used. Based on the thermionic emission model, the forward current density at V > 3kT/q has the form [11] ... [Pg.135]

Similarly, in a metal/semiconductor junction, in which the metal work function lies between the valence band maximum and the conduction band minimum, the tails of the metallic wave function decrease exponentially in the adjacent semiconductor gap states, inducing transfer of charge, which in turn creates the dipole. The mismatch between the metal Fermi level and E is reduced by this dipole (by a factor inversely proportional to the semiconductor s optical dielectric constant, s o, in first approximation [51]). Only in the case of semiconductors with a large optical dielectric constant or high density of interface states is the Fermi level almost completely pinned at E- In this case, since E is an intrinsic property of the semiconductor, the Schottky barrier height of a particular semiconductor is independent of the metal (and its work function) utilized as contact. In order to define the CNL, one... [Pg.799]

The height of the potential barrier decreases with the decrease of the transfer distance. Therefore, the contribution of the transitions between excited vibrational states increases and so does the transition probability. However, short-range repulsion between the reactants increases with a decrease of R, and the reaction occurs at an optimum distance R which is determined by the competition of these two factors. In principle, we may imagine the situation when the optimum distance R corresponds to the absence of a potential barrier for the proton. However, we should keep in mind that the transitions between certain excited states may become entirely adiabatic at short distances.40,41 In this case, the further increase of the transition probability with the decrease of R becomes quite weak, and it cannot compensate for the increased repulsion between the reactants, so that even for the adiabatic transition, the optimum distance R may correspond to sub-barrier proton transfer. [Pg.130]

At high electrolyte concentrations the films become so thin that they loose ability to reflect light there are the so-called common black films. In addition to that, an increase in electrolyte concentration results in a decrease of the height of potential barrier which preserves the film in the state of this metastable equilibrium, i.e., film stability decreases. Thermal oscillations of interface, i.e., the Mandel shtam waves (See Chapter VI, 1), help the system to overcome a potential barrier. If other stabilizing factors are absent, such (local) overcoming of potential barrier results in film rupture. [Pg.550]


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