Chemical dynamics from the gas‐phase to surfaces

The field of gas‐phase chemical dynamics has developed superb experimental methods to probe the detailed outcome of gas‐phase chemical reactions. These experiments inspired and benchmarked first principles dynamics simulations giving access to an atomic scale picture of the motions that underlie these reactions. This fruitful interplay of experiment and theory is the essence of a dynamical approach perfected on gas‐phase reactions, the culmination of which is a standard model of chemical reactivity involving classical trajectories or quantum wave packets moving on a Born–Oppenheimer potential energy surface. Extending the dynamical approach to chemical reactions at surfaces presents challenges of complexity not found in gas‐phase study as reactive processes often involve multiple steps, such as inelastic molecule‐surface scattering and dissipation, leading to adsorption and subsequent thermal desorption and or bond breaking and making. This paper reviews progress toward understanding the elementary processes involved in surface chemistry using the dynamical approach. Key points The fruitful interplay between chemistry and physics leads to an atomic scale view of reactions taking places at catalytically active surfaces. Improved observations of chemical reactions taking place in complex environments drive the development of new approaches to theoretical chemistry. Complex reaction networks from real catalysts are boiled down to their elementary steps and examined from first principles.