FORTRESS: F block cOvalency and Reactivity defined by sTructural compRESSibility

Lead Research Organisation: University of Manchester
Department Name: Chemistry

Abstract

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Description Covalency - a form of chemical bonding - is complex yet central to our understanding of chemistry, particularly in the actinide series. In this project, we have developed and applied state-of-the-art computational methods to gain exquisite understanding of the covalency in the actinide-element bond using three methods: Natural Bond Orbitals (NBO), the Quantum Theory of Atoms in Molecules (QTAIM) and Interacting Quantum Atoms. The latter was used for the first time for actinides other than uranium, in order to assess its applicability in a whole family of elements. It is found to have excellent correlation with NBO and QTAIM covalency metrics, making it a promising addition to the computational toolkit for analysing metal-element bonding. The particular family of molecules we studied to assess covalency were isostructural d and f transition element compounds M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np). Our range of computational metrics agree that the actinide-oxygen bonds are the most covalent of the elements studied, with those of the heavier group 4 elements the least. Within the early actinide series, Th stands apart from the other three elements considered, being consistently the least covalent.

The principal aim of the computational part of this joint experiment-theory collaboration was to develop and apply tools to assess the covalency in actinide-element bonding as a function of pressure. This objective has been met, and several research papers have been published which set out and apply the computational approach we have developed. Achievement of the broader aims of the experiment-theory collaboration remains in progress - although the award has finished, the researchers are very active in analysing and writing up our data for publication. When those papers are published, the aims of the collaboration will also have been met.
Exploitation Route The computational tools we have developed will most certainly be adopted by the wider community of scientists studying the chemical bonding in the actinide series of elements.
Sectors Energy
 
Description Conference talk - "The Effects of Pressure on An-O Bonding: A QTAIM and NBO Study" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Research presentation by Dr Victoria Berryman at the International Conference on the f-Elements (ICFE), Lausanne, Switzerland, September 2018
Year(s) Of Engagement Activity 2018
 
Description Conference talk - "The Effects of Pressure on An-O Bonding: A QTAIM and NBO Study" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Conference talk by Dr Victoria Berryman at the International Conference on DFT and its Applications, Alicante, Spain, July 2019
Year(s) Of Engagement Activity 2019
 
Description Schools' lecture (Birmingham) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact Lecture to A level students on the periodic table, with focus on fundamental f element chemistry, and the problem of the long term fate of the UK's PuO2 stockpile.
Year(s) Of Engagement Activity 2017
URL http://www.wmctc.co.uk/Programme%2017-18.html#21nov