PhD Studentship: Probing Covalency in Actinide Molecules: A Computational Toolbox for Magnetic Resonance

The University of Manchester

Supervisory Team

Primary Supervisor:
 Nicholas Chilton
School / Division: School of Chemistry
% of supervisory split (0-100%): 60

Co-Supervisor 1: Eric McInnes
School / Division: School of Chemistry
% split (0-100%): 20

Co-Supervisor 2: Ralph Adams
School / Division: School of Chemistry
% split (0-100%): 20

Project Details

Funding source: STFC/MOD
Amount awarded for: 
£14777 (stipend)
Expected student start date: 
September 2018
Duration: 3 years

Anticipated start date: September 2018

Project Description

Understanding, predicting, and controlling the behaviour of actinide (An) ions in solution and the solid state is crucial to keeping the nuclear energy option open and in the management of spent fuel. This necessitates fundamental understanding of An chemistry, wherein a central question is the extent of covalent bonding in An compounds. The chemistry of An elements has progressed more slowly than for the other elements, largely due to their inherent radiotoxicity. The advancement of computational techniques is an excellent route to circumvent expensive and hazardous experiments, however there are simply not enough experimental measures of fundamental concepts like covalency, and without such data, computational methods cannot be validated.

Two techniques that can report on the covalency of An species are nuclear magnetic resonance (NMR) and pulsed electron paramagnetic resonance (EPR). Both techniques are able to measure hyperfine interactions (electron spin – nuclear spin) between the An electrons and the ligand nuclei, which can be interpreted as the amount of An spin density on the ligands. This is a direct measure of covalency, and we have recently published the first pulsed EPR study of An materials (A. Formanuik et al., Nature Chem., 2017, 9, 578), demonstrating this approach. However, the data analysis is not trivial and thus we need reliable methods for calculating An hyperfine interactions.

Current approaches are usually based on density functional theory (DFT), which may be inappropriate for An molecules. Therefore, this project aims to develop a toolbox for calculating hyperfine interactions using complete active space self-consistent field (CASSCF) theory, to provide a more accurate electronic structure. The successful candidate will: (i) learn CASSCF and how to determine the electronic structure of An complexes, (ii) aid in developing a method for accurate calculation of hyperfine interactions, and (iii) benchmark computational results by modelling experimental NMR and EPR data.

Related references

Formanuik et al., Nature Chem., 2017, 9, 578

Contact for Further Information

Dr Nicholas F. Chilton

Academic Background of Candidates

Applicants are expected to hold, or about to obtain, a minimum upper second class undergraduate degree (or equivalent) in Chemistry and/or Physics. A Masters degree in a relevant subject and/or experience in computational chemistry is desirable.  

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