Maximum tunneling probability

Based on C-H versus C-D zero point vibrational differences, the authors estimated maximum classical kinetic isotope effects of 17, 53, and 260 for h/ d at -30, -100, and -150°C, respectively. In contrast, ratios of 80,1400, and 13,000 were measured experimentally at those temperatures. Based on the temperature dependence of the atom transfers, the difference in activation energies for H- versus D-abstraction was found to be significantly greater than the theoretical difference of 1.3kcal/mol. These results clearly reflected the smaller tunneling probability of the heavier deuterium atom. 

A further point of interest regarding this problem has been raised by Bell et al. (1971). Calculations based on an electrostatic charge cloud model indicate that the variation in kH/kD is primarily determined by the tunnel correction. Different reactions will have different barrier widths, hence different tunneling probabilities, and, in the context of this hypothesis, different variations of isotope effects. The hypothesis still predicts, however, that for a given system kH/kD will have maximum value for the symmetrical transition state where the probability of tunneling is highest. 

From the very simple WKB considerations it is clear that the tunneling rate is proportional to the Gamov factor exp —2j[2(F(s(0) — )] ds, where s Q) is a path in two dimensions Q= 61)62 ) connecting the initial and flnal states. The most probable tunneling path , or instanton, which renders the Gamov factor maximum, represents a compromise of two competing factors, the barrier height and its width. That is, one has to optimise the instanton path not only in time, as has been done in the previous section, but also in space. This complicates the problem so that numerical calculations are usually needed. 

Plot these results on log-probability coordinates and estimate the mean and standard deviation for each distribution (see Appendix C). What kind of averages are these quantities How do the weekend and weekday particle size distributions compare with respect to the location and width of the maximum The weekend results are attributed to automobile exhaust, whereas the weekday results are assumed to be diluted by aerosols from outside the tunnel. 

Since the probability amplitude for tunneling is exponentially sensitive to the position of the dot, the maximum of the tunnel exchange interaction between an electron on the dot and an electron in one lead occurs when the tunneling coupling to the other lead is negligible. This is why we will assume the following property of tunneling amplitude ALjR t) to be fulfilled ... 

The wave functions for u = 0 to 4 are plotted in figure 6.20 the point where the function crosses through zero is called a node, and we note that the wave function for level v has v nodes. The probability density distribution for each vibrational level is shown in figure 6.21, and the difference between quantum and classical behaviour is a notable feature of this diagram. For example, in the v = 0 level the probability is a maximum at y = 0, whereas for a classical harmonic oscillator it would be a minimum at v = 0, with maxima at the classical turning points. Furthermore the probability density is small but finite outside the classical region, a phenomenon known as quantum mechanical tunnelling. 

---