PhD Studentship in Computational Chemistry: Electronic Structure and Bonding in Molecular f Element Chemistry

The University of Manchester

Supervisor: Prof Nik Kaltsoyannis, School of Chemistry
Email: nikolas.kaltsoyannis@manchester.ac.uk
Research group website: http://www.mub.eps.manchester.ac.uk/kaltsoyannisgroup/
Centre for Radiochemistry Research website: http://crr.manchester.ac.uk/

Anticipated start date for project: 18 September 2017

Project Summary

Background

The f block is vital to modern society. The 4f (lanthanide) elements lie at the heart of many key technologies, e.g. phosphors and lighting (europium); high-strength magnets for electronics, hybrid vehicles and wind turbines (neodymium); optoelectronics (neodymium, erbium); magnetic resonance imaging (gadolinium); automobile catalytic converters (cerium). The 5f (actinide) series features two elements (uranium and plutonium) that are central to nuclear power production. We therefore need to know as much as we possibly can about the chemistry of these fascinating elements.

This PhD project will employ computational chemistry based on high‑level ab initio wavefunction theory to gain detailed understanding of the electronic structure and bonding in molecules containing f elements. The computational chemistry of the f block remains challenging, for two principal reasons: (i) relativistic effects (the modification of atomic orbital energies vs non‑relativistic analogues, and spin-orbit coupling) - which can either be neglected or accommodated with only simple approximations and corrections for light atoms - have a significant effect on 4f and 5f element chemistry, and must be explicitly included in calculations, and (ii) the near degeneracy of several sets of valence atomic orbitals (e.g. for the actinides 5f, 6d, 7s and 7p) can lead to a plethora of closely-spaced electronic states which pose formidable electron correlation challenges. In this project you will learn how modern computational chemistry can overcome these challenges, and apply your skills to cutting‑edge problems in molecular f element chemistry.

The project

The initial focus of the research will be molecules of general formula EAnF3, where E = N, P, As, Sb and Pb and An = U, Np and Pu. NUF3, PUF3 and AsUF3 are known experimentally from matrix isolation studies [Inorg. Chem. 48 (2009) 6594], and previous calculations have suggested that they feature triple bonds between U and the group 15 element. However, other electronic states involving unpairing of the electrons in the triple bond are computed to lie very close in energy to the triple bond state, and may have a better match with experimental vibrational spectroscopy data. Thus the true ground state and bonding in these systems is not known for sure, and establishing these will form the initial target of this research. Extension to heavier group 15 elements and actinides will shed further light on these systems, especially the interplay of metal‑ and pnictogen‑centred spin‑orbit coupling in the heavier group 15 compounds.

The subsequent focus of the research is not fixed at this stage, giving the successful applicant the opportunity to develop and explore their own interests in molecular f element chemistry.

Qualification

Applicants should have or expect a good (I or II(i)) honours degree (or an equivalent degree) in Chemistry.

Funding

The current stipend for 2016/17 is 14,296 pound sterling. The stipend for September 2017 is yet to be confirmed but will be offered at the RCUK rate. Eligibility: Due to funding restrictions the studentship is available to UK and EU nationals only.

Further Information

Please contact Professor Nik Kaltsoyannis (Email - nikolas.kaltsoyannis@manchester.ac.uk) for further information. A formal application must be submitted to be considered.

How to apply

Complete an online application form using the following web link http://www.manchester.ac.uk/postgraduate/howtoapply/

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Type / Role:

PhD

Location(s):

Northern England