Post-doctoral researchers
Dr Song Yu
Radicals are highly reactive and ideal for building complex compounds. Samarium(II) diiodide, SmI2, also known as Kagan’s reagent, is a classic single electron transfer (SET) reagent that can efficiently produce radical species and mediate chemical processes that no other reagent can. It is a crucial catalyst in organic synthesis and one of the most significant SET reagents. However, a well-known drawback of SmI2, i.e., it must always be used in stoichiometric excess, raises issues of cost and waste and impedes its application in industry. Recently, the group of Prof. David J. Procter developed SmI2-catalysed reactions through radical relays that only need a catalytic amount of reagent. In these reactions, SET from SmI2 converts the substrate to a radical, which then undergoes radical relocation, bond-formation, new radical generation, and radical back-donation to regenerate the catalyst. Song uses density functional theory calculations and quantum chemical analyses to better understand the mechanisms driving these catalytic coupling reactions and radical relays.
Dr Shahbaz Ahmad
Shahbaz is at the forefront of sustainable energy research through an EPSRC funded collaboration with Prof Polly Arnold’s team at the University of California, Berkeley. Having earned his PhD in computational chemistry at St Andrews, focusing on computational mechanistic studies of transition metal homogeneous catalysts, and with additional experience from Brookhaven National Laboratory, Shahbaz is a key contributor to this project. This partnership aims to improve our understanding of catalyst behaviour and develop experimental strategies for the efficient conversion of nitrogen to ammonia and secondary or tertiary amines. Committing to annual visits to Berkeley, he bridges the gap between computational findings and experimental work, underscoring the UK’s role in advancing global sustainable chemistry research.
PhD students
Ryan Dempsey
The Enhanced Actinide Removal Plant (EARP) at Sellafield has been the UK’s most crucial radioactive effluent treatment plant since its operation began in 1994. The EARP removes actinides and other fission products by association with ferrous mineral phases during a base-induced precipitation process. The same process was also used to aid the clean-up operations after the 2011 Fukushima Daiichi disaster. Unfortunately, the mechanism by which the actinides associate with the iron-bearing minerals is unknown. It has been observed that during the process Pu(IV) may bind to a Keggin type Fe(III) nanocluster with further evidence that the Keggin unit is a prenucleation cluster during ferrihydrite formation. Ryan will use molecular quantum chemical techniques based on open-shell Density Functional Theory to investigate the bonding interactions and redox chemistry between actinides and this Keggin cluster. Starting with Pu(IV), and exploring other actinides found at the EARP, Ryan aims to provide a better understanding of the processes underpinning nuclear waste clean-up to inform future efforts.
Corinne Hatton
The long-term storage of high level spent nuclear fuel is a problem in the UK and worldwide, and one potential solution is to design and employ geological disposal facilities (GDFs). In these facilities it is crucial that the uranium and other actinide species are unable to migrate into the geosphere. To design GDFs, the interactions between actinide species and minerals surfaces at an atomic scale need to be understood and a comprehensive model developed. Iron (II) minerals are being researched specifically due to their abundance and ability to react with uranium species. Corinne’s research will be studying the interaction, chemical bonding and REDOX transformations of aqueous uranium species with iron minerals. This research will use hybrid DFT within the Periodic Electrostatic Embedded Cluster Method (PEECM) with accompanying experimental studies with the Natrajan group here in Manchester.
Josef Tomecek
Metal-metal bonding between actinide elements was a rather rare phenomenon limited to a small number of species stable in the gas phase at very low temperatures. This was recently changed by Liddle and Kaltsoyannis’ report of a tri-thorium cluster [{Th(η8‑C8H8)(μ3‑Cl)2}3{K(THF)2}2]∞. In his PhD project, Josef uses both DFT and ab initio methods to shed light on actinide-actinide bonding. Starting with the parent tri-thorium cluster, the next steps will lead to the exploration of other systems that may be eventually prepared and/or to the study of other compounds synthesised by Liddle’s group.
Anlu (Tara) Wei
Nuclear fuel is typically uranium dioxide. During its lifetime in reactors, some of the uranium converts to plutonium by radioactive decay. After the spent fuel is removed from UK reactors, the plutonium is separated out, and is currently placed in interim storage pending a Government decision as to its long-term fate, which may well be burial in a geological disposal facility (GDF). A prospective GDF wasteform material for hosting plutonium is zirconolite. To evaluate the long-term performance of potential wasteforms, it is crucial to understand the effects of the radioactive decay of the plutonium. This decay produces helium, the release of which inside the wasteform can lead to the formation of bubbles and cracking, and hence to decreased durability. Tara’s PhD project is therefore a comprehensive computational study of the behaviour of helium in zirconolite. Density functional theory and molecular dynamics simulation will be employed to investigate the migration of helium in zirconolite as well as the thermodynamics and kinetics of helium bubble formation.
Celina Hjort Buhl
SmI2 is a versatile resultant in organic chemistry, and its use in organic radical catalysis is a new area worthy of deeper exploration. The SmI2 is typically modelled computationally with THF ligands making up its primary coordination shell, but it is not yet known how accurate that model is – other ligands such as water or HMPA may well displace one or more THF in catalytic reactions. The initial purpose of Celina’s MPhil project is to take previously modelled, and possibly new, reactions and explore the effects of replacing one or more THF ligands with water or HMPA.
Daniel Galano
The industrial production of chemicals accounts for £34 Bn within the UK manufacturing sector, and up to 90% of chemical products require the use of a catalyst at some point in their preparation. However, these catalysts are often based on expensive, non-renewable precious metals, the use of which is associated with many environmental and geopolitical issues. Hence the development of alternative catalysts based on abundant main group elements, such as phosphorus, is increasingly urgent. The group of Dr Meera Mehta has recently found that [P7] Zintl clusters are competent heterogenous catalysts for a variety of organic transformations. However, as these applications are in their infancy, greater mechanistic understanding is required to optimise existing transformations and propose new ones. Therefore, the purpose of Daniel’s PhD project is to use DFT methods to better understand the mechanisms by which these main group clusters catalyse organic transformations, and thus facilitate the new design of improved sustainable-element catalysts.