Chemical Reactions and Mechanisms

Quantum tunneling allows atoms and molecules to pass through energy barriers rather than over them, and chemists have increasingly recognized that this effect shapes not just hydrogen transfer reactions but also rearrangements involving heavier atoms like carbon and nitrogen. The study of tunneling control examines how, at low temperatures in particular, tunneling can determine which product a reaction produces—sometimes overriding the classical prediction entirely—with nitrenes and carbenes serving as especially informative test cases because their reactive intermediates can be trapped and studied in matrix isolation experiments. Understanding when and how heavy-atom tunneling governs reaction outcomes matters for organic synthesis, where controlling selectivity is paramount, and for astrophysical chemistry, where reactions proceed in cold environments where classical barriers would otherwise halt them. Active work is focused on developing computational methods accurate enough to predict tunneling rates for larger molecules and on designing reactions where tunneling control can be deliberately exploited rather than merely observed.

Works

43,870

Total citations

285,231

Keywords

Tunneling ControlChemical ReactionsNitrenesCarbenesPhotochemistryOrganic Synthesis