Vibrational control of the reaction pathway in the H + CHD<sub>3</sub> → H<sub>2</sub> + CD<sub>3</sub> reaction.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 35353570.
- Also identified by DOI 10.1126/sciadv.abm9820 and PMC identifier 8967217.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
An accurate full-dimensional quantum state-to-state simulation of the six-atom title reaction based on first-principles theory is reported. Counterintuitive effects are found: Increasing the energy in the reactant's CD<sub>3</sub> umbrella vibration reduces the energy in the corresponding product vibration. An in-depth analysis reveals the crucial role of the effective dynamical transition state: Its geometry is controlled by the vibrational states of the reactants and subsequently controls the quantum state distribution of the products. This finding enables generalizing the concept of transition state control of chemical reactions to the quantum state-specific level.