Signatures of nonadiabatic O2 dissociation at Al(111): First-principles fewest-switches study

TL;DR

This study investigates how nonadiabatic spin transitions influence O2 dissociation on Al(111) surfaces using first-principles simulations, highlighting their potential experimental detectability and impact on reaction dynamics.

Contribution

It introduces a first-principles approach to analyze nonadiabatic spin transitions in O2 dissociation on Al(111), emphasizing their role in reaction dynamics and experimental observability.

Findings

Spin transitions significantly affect dissociation probabilities.

Proposed experimental setups can detect spin transition effects.

Nonadiabatic effects explain discrepancies in previous measurements.

Abstract

Recently, spin selection rules have been invoked to explain the discrepancy between measured and calculated adsorption probabilities of molecular oxygen reacting with Al(111). In this work, we inspect the impact of nonadiabatic spin transitions on the dynamics of this system from first principles. For this purpose the motion on two distinct potential-energy surfaces associated to different spin configurations and possible transitions between them are inspected by means of the Fewest Switches algorithm. Within this framework we especially focus on the influence of such spin transitions on observables accessible to molecular beam experiments. On this basis we suggest experimental setups that can validate the occurrence of such transitions and discuss their feasibility.