title: Isomerism of Trimeric Aluminum Complexes in Aqueous Environments: Exploration via DFT-Based Metadynamics Simulation.
abstract: The chemistry of aluminum or oxo-aluminum in water is still relatively unknown, although it is the basis for many chemical and industrial processes, including flocculation in water treatment plants. Trimeric species have a predominant role in the formation of the Keggin cations, which are the basic building blocks of aluminum-based chemicals. Despite this, details of the structural evolution of these small solvated clusters and how this is related to the processes leading to the formation of larger aggregates are still an open issue. To address these questions, here, we have applied the metadynamics (MTD) simulation technique [ Barducci , A. ; Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2010 , 1 , 826 - 843 ] with density functional theory-based molecular dynamics to disclose the dynamics and structural conversions of trimeric aluminum complexes in an aqueous environment. The existence of a variety of competing metastable conformations, for example, book-like, cyclic boat, and linear shape conformations, is revealed in the MTD simulation. Furthermore, equilibrium simulations of the various intermediate states encountered along the MTD trajectory are used to assess their (meta)stability, determine the rearrangement of the OH ligands, and discuss the role of the solvating water.
authors: Thule-Institute, University of Oulu , P.O. Box 7300, FI-90014 University of Oulu, Finland.
authors: Giorgio
authors: G
authors: Lanzani
authors: Institut für Chemie, University of Zurich , Winterthurerstrasse 190, CH-8057 Zurich, Switzerland.|Département de Chimie, École Normale Supérieure , 24 rue Lhomond, F-75005 Paris, France.
authors: Ari P
authors: AP
authors: Seitsonen
authors: Institut für Chemie, University of Zurich , Winterthurerstrasse 190, CH-8057 Zurich, Switzerland.
authors: Marcella
authors: M
authors: Iannuzzi
authors: Department of Chemistry, Aalto University , P.O. Box 16100, FI-00076 Aalto, Finland.
authors: Kari
authors: K
authors: Laasonen
authors: Department of Environmental and Biosciences, University of Eastern Finland , PL 1627, FI-70211 Kuopio, Finland.
authors: Simo O
authors: SO
authors: Pehkonen