Potential Energy Surfaces for the Dynamics of Elementary Gas-Surface Processes

Cutting a chemical bond with demon's scissors: Mode- and bond-selective reactivity of methane on metal surfaces

“…Now, various methods exist for constructing reliable 6D PES for the dissociative adsorption of diatomic molecules on solid surfaces (see e.g., Refs. [20] and [21] as well as references therein). However, many successful methods for constructing PES of diatomic molecules, in particular those based on interpolation, can be hardly extended to deal with PES of higher dimensionality.…”

New Potential Energy Surface for the H + Cl2 Reaction and Quantum Dynamics Studies

“…Such simplification was known to lead to limitations in accurately capturing the full complexity of atomic interactions. 19,25 The first ab initio PES (named POLCI) for the HCl 2 system was developed by Garrett et al, 26 who fitted 15 ab initio points for collinear geometries (Cl−H−Cl) to a cubic spline function and 6 ab initio points for bent geometries to a quadratic− quartic analytical function. Subsequently, Maierle et al 27 presented an ab initio PES (named MSGMC) based on a cubic spline fit to 223 ab initio points calculated at the level of the multiconfiguration self-consistent field.…”

“…Nevertheless, these semiempirical PESs were simplified models developed under the assumption that any three-atom interaction could be represented by an analytical expression with a limited set of adjustable parameters. Such simplification was known to lead to limitations in accurately capturing the full complexity of atomic interactions. , …”