Tunneling and Tunneling Switching Dynamics in Phenol and Its Isotopomers from High-Resolution FTIR Spectroscopy with Synchrotron Radiation

摘要

The tunnel effect in chemical reactions is one prominent example where it is obvious that the classical molecular dynamics description for chemistry and biochemistry has to be amended by quantum dynamical effects. Some recent prototypical and well-studied examples include tunneling in (HF)2 rearrangements, mode selective control of stereo-mutation kinetics in HOOH, and further prototypical reactions such as OH + CO and kinetic control by tunneling in methylhydroxycarbene. A particularly intriguing recent development is the theoretical prediction of tunneling switching in ClOOCl. Here, at low energy, tunneling is completely suppressed by a very slight but dominant asymmetry arising from electroweak parity violation, which effectively localizes the molecular wavefunction at the structure of one enantiomer at low energies.