Vibrational control of the reaction pathway in the H + CHD <sub>3</sub> → H <sub>2</sub> + CD <sub>3</sub> reaction
Roman Ellerbrock, Bin Zhao, Uwe Manthe
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 3 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.
Topics & Concepts
State (computer science)Atomic physicsAtom (system on chip)QuantumProduct (mathematics)Transition state theoryChemical reactionChemistryQuantum chemicalPhysicsPhysical chemistryQuantum mechanicsReaction rate constantMoleculeMathematicsGeometryComputer scienceKineticsBiochemistryEmbedded systemAlgorithmSpectroscopy and Quantum Chemical StudiesAdvanced Chemical Physics StudiesSpectroscopy and Laser Applications