Atom Tunneling in Chemistry

Abstract

Quantum mechanical tunneling of atoms is increasingly found to play an important role in many chemical transformations. Experimentally, atom tunneling can be indirectly detected by temperature-independent rate constants at low temperature or by enhanced kinetic isotope effects. In contrast, the influence of tunneling on the reaction rates can be monitored directly through computational investigations. The tunnel effect, for example, changes reaction paths and branching ratios, enables chemical reactions in an astrochemical environment that would be impossible by thermal transition, and influences biochemical processes.

Eyringpy: A program for computing rate constants in the gas phase and in solution

“…However, in some cases, it is mandatory to take into account other factors that can affect the accuracy of the computed rate constants. TST is intrinsically classical, thus inclusion of the quantum‐mechanical phenomena, like tunneling, is important for reactions that involve the transference of small mass particles or with narrow barriers, especially at low temperatures . Conversely, for reactions in solution, rate constants also depend on several aspects, such as the polarity and viscosity of the solvent in which the reaction is carried out.…”

Duisberg Memorial Award: F. Schacher / Gmelin–Beilstein Memorial Medal: G. Restrepo / Ostwald Early Career Award: J. Meisner / Baizer Award: S. Waldvogel

“…As a postdoctoral researcher in the group of Todd Martínez at Stanford University and Stanford Linear Accelerator Center, Meisner is currently working on the automated exploration of chemical reaction networks and the connection to microkinetic modelling. Together with Johannes Kästner, Meisner has published a Review in Angewandte Chemie on atom tunneling in chemistry …”

Variational principle for the determination of unstable periodic orbits and instanton trajectories at saddle points

“…[15][16][17][18][19][20][21][22][23] A general distinction can be made between stable and unstable POs. Integrable systems give rise to POs whose oscillations on the invariant tori can be characterized by corresponding particular frequencies.…”