Tunneling zero-point

The square of the wavefunction is finite beyond the classical turrfing points of the motion, and this is referred to as quantum-mechanical tunnelling. There is a further point worth noticing about the quantum-mechanical solutions. The harmonic oscillator is not allowed to have zero energy. The smallest allowed value of vibrational energy is h/2jt). k /fj. 0 + j) and this is called the zero point energy. Even at a temperature of OK, molecules have this residual energy. 

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. 

One of the simplest chemical reactions involving a barrier, H2 + H —> [H—H—H] —> II + H2, has been investigated in some detail in a number of publications. The theoretical description of this hydrogen abstraction sequence turns out to be quite involved for post-Hartree-Fock methods and is anything but a trivial task for density functional theory approaches. Table 13-7 shows results reported by Johnson et al., 1994, and Csonka and Johnson, 1998, for computed classical barrier heights (without consideration of zero-point vibrational corrections or tunneling effects) obtained with various methods. The CCSD(T) result of 9.9 kcal/mol is probably very accurate and serves as a reference (the experimental barrier, which of course includes zero-point energy contributions, amounts to 9.7 kcal/mol). 

Wong K-Y, Gao J (2008) Systematic approach for computing zero-point energy, quantum partition function, and tunneling effect based on Kleinert s variational perturbation theory. J Chem Theory Comput 4(9) 1409-1422... 

The QFH potential approximately captures two key quantum effects. When an atom is near a potential minimum, the curvature is positive and thus so is the QFH correction this models the zero-point effect. On the other hand, near potential maxima the curvature is negative, and the QFH potential models tunneling. 

Thnnelling has sometimes been regarded as a mysterious phenomenon by chemists. It is worth stressing, therefore, that tunnelling has the same firm foundation in quantum mechanics as zero-point energy, which is the most important component of a KIE both these phenomena are a consequence of Heisenberg s uncertainty principle. 

Because of their dependence on mass, KIEs have been used in two ways to detect tunnelling. One is that primary deuterium KIEs are larger than predicted on the basis of zero-point energy alone when tunnelling makes a significant contribution to the KIE. For example, primary deuterium KIEs larger than 25 have been reported (Lewis and Funderburk, 1967 Wilson et al., 1973) for proton transfer reactions where tunnelling is important. 

Qualitatively the results are explained in the following way. Although the transferring deuterium atom does not introduce a primary isotope effect due to zero-point energy differences into ko/ko, there is less tunnelling when deuterium is transferred than when hydrogen is transferred. Therefore, the tunnel correction to the secondary /c°//cd is small relative to that for k /k. Thus, the experimental results are in agreement with the results of the model calculations. 

Finally, it is important to realize that the application of several criteria is advisable if reliable estimates of tunnelling are to be obtained. Just one criterion, e.g. the magnitude of the secondary KIE, may be misleading since a large KIE may be the result of a small tunnelling contribution and a large zero-point energy contribution. 

Fig. 4.5 Schematic projection of the energetics of a reaction. The diagram shows the Born-Oppenheimer energy surface mapped onto the reaction coordinate. The barrier height AE has its zero at the bottom of the reactant well. One of the 3n — 6 vibrational modes orthogonal to the reaction coordinate is shown in the transition state. H and D zero point vibrational levels are shown schematically in the reactant, product, and transition states. The reaction as diagrammed is slightly endothermic, AE > 0. The semiclassical reaction path follows the dash-dot arrows. Alternatively part of the reaction may proceed by tunneling through the barrier from reactants to products with a certain probability as shown with the gray arrow...

Fig. 10.1 Zero point energy diagrams, (a) An H or D atom attacking an H2 molecule. The TST isotope effect is negative (inverse, kn > kn) because there is no zero point isotope effect in the ground state, and tunneling is ignored in the TST approximation, (b) An H atom attacking either an H2 or D2 molecule. The isotope effect calculated in the TST approximation is positive (normal, kH > kn) because the zero point isotope effect in the ground state is larger than that in the transition state.

Non-unit kinetic isotope effects such as the rate-constant ratio kn/k-Q also derive from isotopic zero-point energy differences in the reactant state and in the transition state. A second manifestation of the Uncertainty Principle may also contribute to kinetic isotope eff ects, namely isotopic differences in the probability of quantum tunneling through the energy barrier between the reactant state and the product state. 

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