Global optimization of clusters using electronic structure methods

TLDR

Global optimization of cluster structures using first‑principles electronic structure methods has grown rapidly, driven by the need to avoid empirical potentials and enabled by advances in search algorithms, computational efficiency, and high‑performance computing. This review surveys global optimization algorithms—particularly genetic algorithms and basin hopping—emphasizing their implementation with electronic structure methods, especially DFT, and outlines potential future directions. The authors describe how genetic algorithms and basin‑hopping techniques are implemented with density functional theory to search for global‑minimum cluster structures. Illustrative applications demonstrate the method’s applicability to isolated monometallic and bimetallic clusters, molecular clusters, and ligated or surface‑supported metal clusters. © 2013 Wiley Periodicals, Inc.

Abstract

Over the past decade, there has been a significant growth in the development and application of methods for performing global optimization (GO) of cluster and nanoparticle structures using first‐principles electronic structure methods coupled to sophisticated search algorithms. This has in part been driven by the desire to avoid the use of empirical potentials (EPs), especially in cases where no reliable potentials exist to guide the search toward reasonable regions of configuration space. This has been facilitated by improvements in the reliability of the search algorithms, increased efficiency of the electronic structure methods, and the development of faster, multiprocessor high‐performance computing architectures. In this review, we give a brief overview of GO algorithms, though concentrating mainly on genetic algorithm and basin hopping techniques, first in combination with EPs. The major part of the review then deals with details of the implementation and application of these search methods to allow exploration for global minimum cluster structures directly using electronic structure methods and, in particular, density functional theory. Example applications are presented, ranging from isolated monometallic and bimetallic clusters to molecular clusters and ligated and surface supported metal clusters. Finally, some possible future developments are highlighted. © 2013 Wiley Periodicals, Inc.