高等有机化学-chapter03.pptVIP

3.5.5 The tunnelling effect Occasionally a PKIE is far in excess of the maximum value ( kH/kD = 7~8 ) at a given temperature. For example, Me2C–NO2 + + R = CH3 R = H kH/kD : 24 9 . . kH/kD : 13000 * Quantum-Mechanical Tunnel Effects ? de Broglie wavelength λ= h mv Particle: e- H D T C Br λ(pm) : 2690 63 45 36 18 7 Ea ? E x TS m ? Hesisenberg Uncertainty Principle DX ? DPx ≥ h for proton, DX ≈ h 4p ≈ 5 (pm) ? Low temperature ? narrow energy barrier ? solvation ? rare phenomenon. 3.5.6 Solvent isotope effects (SIE)