Metadynamics as a Tool for Exploring Free Energy Landscapes of Chemical Reactions

• Published in: Accounts of chemical research Vol. 39; no. 2; pp. 73 - 81
• Main Authors: Ensing, Bernd, De Vivo, Marco, Liu, Zhiwei, Moore, Preston, Klein, Michael L
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 01-02-2006
• ISSN: 0001-4842; 1520-4898
• DOI: 10.1021/ar040198i

The metadynamics or hills method is a relatively new molecular dynamics technique aimed to enhance the sampling of separated regions in phase space and map out the underlying free energy landscape as a function of a small number of order parameters or collective variables. The high efficiency allows for the application of metadynamics in combination with first principles dynamics methods, in particular with Car−Parrinello molecular dynamics, to study processes in which changes in the electronic structure play a dominant role, such as chemical reactions. The option to choose several independent collective variables is important to tackle complex and concerted transformations that lack an obvious a priori choice for a single reaction coordinate. In this Account, we discuss the role of metadynamics in the search of transition states, local minima, reaction paths, free energy profiles, and reaction coordinates among a growing list of alternative methods.