Journal
ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS
Volume 227, Issue 9-11, Pages 1523-1542Publisher
WALTER DE GRUYTER GMBH
DOI: 10.1524/zpch.2013.0410
Keywords
PES; Gas-Surface Dynamics; Dissociative Sticking Probability; Corrugation-Reducing Procedure; Neural Networks; Global Minima Search
Categories
Ask authors/readers for more resources
In honoring the seminal contribution of Henry Eyring and Michael Polanyi who first introduced the concept of potential energy surfaces (PESs) to describe chemical reactions in gas-phase [Z. Phys. Chem. 12, 279-311, (1931)], this work comes to review and assess state-of-the-art approaches towards first-principle based modeling in the field of gas-surface dynamics. Within the Born-Oppenheimer and frozen surface approximations, the O-2-Ag(100) interaction energetics are used as a showcase system to accentuate the complex landscape exhibited by the PESs employed to describe the impingement of diatomics on metal substrates and draw attention to the far-from-trivial task of continuously representing them within all six molecular degrees of freedom. To this end, the same set of ab initio reference data obtained within Density Functional Theory (DFT) are continuously represented by two different state-of-the-art high-dimensional approaches, namely the Corrugation-Reducing Procedure and Neural Networks. Exploiting the numerically undemanding nature of the resulting representations, a detailed static evaluation is performed on both PESs based on an extensive global minima search. The latter proved particularly illuminating in revealing representation deficiencies which affect the dynamical picture yet go otherwise unnoticed within the so-called divide-and-conquer approach.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available