Density Functional Theory Modelization of Iron Clusters of Biological Relevance


Type of Project: Theory

Location: Donostia

Xabier Lopez

Txema Mercero
Status: closed

The understanding of the role of transition metals in biological systems is key to unveil important aspects of the enzymatic capability of metaloenzymes which contains a metal cluster core. For instance, the iron-sulfur clusters are ubiquitous in biological systems and may be found in the active site of a wide variety of metalloproteins and metalloenzymes, which are involved in biological processes such as electron transfer (ferredoxin), small molecule activation (nitrogenase, hydrogenase, carbon monoxide dehydrogenase), radical-based catalytic transformations (hydrogen abstraction, sulfur insertion in biotin synthase), DNA repair and signal transduction. The most common clusters are the following: [Fe2S2], [Fe3S4] and [Fe4S4], and their primary function lies in the mediation of one-electron redox processes.

In these polymetallic systems, the Fe atoms present several oxidation states with unpaired electrons that can be coupled by magnetic interactions, giving rise to a dense manifold of ferro- and antiferromagnetic electronic states which may be separated by small energy differences. In this way, a detailed knowledge of the electron delocalization in the cluster in terms of Fe-Fe interactions is a key point in order to understand the properties of both the ground and excited states. The goal of this project is to use state-of-the-art DFT to benchmark the performance of these methods to model FeS clusters and their electronic excitations.

The candidate should have a basic knowledge on quantum mechanics (assumed in chemistry and physics BSc. students), and be eager to learn the basics of computational chemistry.