Chemical Applications of Velocity and Spatial Imaging

Lead Research Organisation: University of Bristol
Department Name: Chemistry

Abstract

Ion imaging, first demonstrated just 25 years ago, is already having a major impact on the way we explore molecular change (the very essence of chemistry) in many gas phase systems. The technique has features in common with mass spectrometry (MS). Both start by removing an electron from the target species, generating ions, i.e. charged molecules or fragments, which are then 'sorted' by their mass. In traditional MS, the species of interest is characterised by its spectrum of ion yield versus mass. Electron removal in most ion imaging experiments is induced by a short pulse of laser light; the resulting ions are then accelerated towards a time and position sensitive detector. Heavier ions travel more slowly, so one can image ions of just one particular mass by ensuring that the detector is only 'on' at the appropriate time. The spatial pattern of ion impacts that builds up on the detector when the experiment is repeated many times is visually intuitive, and provides quantitative energetic information about the reaction(s) that yields the monitored product. However, the read out time of current ion imaging detectors is too slow to allow imaging of ions with different mass formed in the same laser shot, and many species are not readily amenable to ionisation in current ion imaging schemes. Imaging all products from a given reaction is therefore time consuming (at best) and, at worst, impossible.
We seek to solve both these limitations. Two of the team have already demonstrated new, much faster, time and position sensitive sensors capable of imaging multiple masses in a single shot experiment. This multimass imaging capability will be developed further and rolled-out for use and refinement across the team. We also propose new multiphoton ionization schemes as well as 'universal' ion formation methods based on use of shorter laser wavelengths or short duration pulses of energy selected electrons. The following over-arching scientific ambitions will proceed in parallel, and exploit the foregoing advances in ion imaging technology at the earliest possible opportunity:
(i) We will use the latest ion imaging methods to explore molecular change in the gas phase, focusing on key families of (photo)chemical reactions: addition, dissociation, cyclisation and ring opening reactions of organic molecules, and metal-ligand and metal-cluster interactions. These choices reflect the importance of such reactions in synthesis, catalysis, etc., their amenability to complementary high level theory, and our ability to explore the same reactions in solution (using a new ultrafast pump-probe laser spectroscopy facility). Determining the extent to which the mechanisms and energetics of reactions established through exquisitely detailed gas phase studies can inform our understanding of reactivity in the condensed phase is a current 'hot' issue in chemical science, which the team is ideally placed to address.
(ii) We will develop and exploit new multi-dimensional analytical methods with combined mass, structural and spatial resolution. Mass spectra usually show many peaks attributable to fragment ions, but the paths by which these are formed are often unclear. Imaging MS is proposed as a novel means of unravelling different routes to forming a given fragment ion; distinguishing and characterising such pathways can offer new insights into, for example, peptide structure. Yet more ambitious, we propose to combine multimass and spatial map imaging with existing laser desorption/ionisation methods to enable spatially resolved compositional analysis of surfaces and of samples on surfaces. Such a capability will offer new opportunities in diverse activities like tissue imaging (e.g. detection of metal ions within tissue specimens of relevance to understanding the failure of some metal-on-metal hip implants), forensic analysis (e.g. 'chemical' imaging of fingerprints, inks, dyes, pollens, etc) and parallel mass spectrometric sampling (e.g. of blood samples).

Planned Impact

Five technical work packages (TWPs) underpinning four substantial scientific work packages (SWPs) are proposed. The TWPs centre on new and improved methods of (i) creating charged particles, (ii) detecting/imaging them with improved velocity, spatial and/or time resolution and (iii) integrated high-level modelling of the results of experiments (photodissociation or photoionization processes, bimolecular reactions, surface desorptions, etc) which depend on such measurements. Short term beneficiaries include the economy (e.g. companies developing and manufacturing improved fast charged particle imaging detectors/sensors, with several of whom consortium members already collaborate). Such devices already find many applications of benefit to society (e.g. monitoring bioluminescence, corona imaging, fluorescence lifetime imaging, time resolved imaging, high speed and/or low light level imaging, security detection systems, threat detection systems, missile warning systems, space science, etc), but the quest for new and improved performance is unending. On the longer term (but within the timescale of the PG), fast sensors of the type envisaged here should offer new opportunities in mass spectrometry (e.g. imaging mass spectrometry) - a pivotal research and analysis tool in broad areas of physical and life science - and more widely (e.g. in neutron science, electron microscopy, etc). Interest in new and improved neutron detectors has soared as a result of the current world shortage of 3He.
Apart from Instrument Development, the proposed SWP activities are envisaged to have longer term impact in several other areas of the EPSRC Portfolio: Healthcare Technologies (e.g. chemical analysis of bioarrays and tissue analysis, enabled by new high fidelity, mass selective, spatially resolved imaging methods), Energy (e.g. via improved understanding of catalytic sites and surfaces from gas phase, gas-surface and condensed phase studies), Manufacturing for the Future (e.g. improved understanding and application of condensed phase (photo)chemical reactivity). The latter SWP also impacts on the Dial-a-Molecule Grand Challenge in Chemistry - by providing a deeper understanding of chemical reactivity and the promise of greater control. Such science boosts the pool of knowledge available to synthetic chemists, the pharmaceutical industry, etc; the strength of associated synthetic chemistry and biochemistry groups at Bristol (which hosts the CDT in Chemical Synthesis) and at Oxford will help ensure efficient knowledge transfer.
Longer term benefits for society in general, the knowledge base and people will be delivered through the training of a new generation of research leaders skilled in quantitative, cutting edge experimental and theoretical physical chemistry/chemical physics, capable of identifying and solving problems of global importance, and by the development and application of novel instrumentation coupled with integrated high-level computational modelling. Recent destinations for group members include academia (e.g. new appointees at UC Irvine, Heriot Watt, Newcastle), post-doctoral research (e.g. UC Berkeley, VU Amsterdam, Berlin, Lausanne, Space Science Group and Diamond Synchrotron at RAL) and industry (e.g. Du Pont, Malvern Instruments, AWE, Shell International).

Publications

10 25 50
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Allum F (2018) Coulomb explosion imaging of CHI and CHClI photodissociation dynamics. in The Journal of chemical physics

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Allum F (2018) Coulomb explosion imaging of CH 3 I and CH 2 ClI photodissociation dynamics in The Journal of Chemical Physics

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Aoiz FJ (2015) A new perspective: imaging the stereochemistry of molecular collisions. in Physical chemistry chemical physics : PCCP

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Ashfold MNR (2017) Molecular Photofragmentation Dynamics in the Gas and Condensed Phases. in Annual review of physical chemistry

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Ashfold MNR (2019) Photoinduced C-H bond fission in prototypical organic molecules and radicals. in Physical chemistry chemical physics : PCCP

 
Description This is a 5 year programme grant award; a detailed (~20 page) end of year 2 progress report was sent to external advisory board members and EPSRC at the start of 2016.
In summary:
PImMS1 cameras are now installed in the labs of 4 of the lead investigators.
After a few teething issues, two of these have been upgraded to the PImMS2 sensor and are running well.
We were able to recruit excellent PDRAs to the PG. One - resigned in 9/2015 to take a permanent scientist position at the Norwegian Institute for Energy Technology. Another has secured an Assistant Professorship at Fort Lewis College, Colorado, starting in summer 2016. Two others left in 2016 to start Teaching Fellow positions at the Universities of St Andrew and Warwick, respectively. The search for their successors attracted a very strong pool of applicants; and two new PDRAs joined the PG in early 2016.
Another 2-year PDRA position is currently being advertised.
Much high quality science has been performed - addressing technique development, unimolecular gas phase molecular photophysics, bimolecular collisions and gas phase reactivity, new developments in mass spectrometry and imaging material on surfaces. Since the start of 2014, the team have published >50 peer reviewed articles on topics within the remit of the PG, in most of the leading journals for work in this area (J. Chem. Phys., J. Phys. Chem. A, J. Phys. Chem. Letts., Chem. Sci., Phys. Chem. Chem. Phys., Phys. Rev. Lett., Phys. Rev. A, Rev. Sci. Instrum., etc. Roughly one third of these publications are authored by more than one of the lead investigators; a similar fraction reports collaborative work with groups outside of the PG.
The lead investigators have given >50 invited conference lectures and a further 30 research seminars on work within the PG remit during the period 2014-16. Each has further invitations lined up for 2017. The PDRAs and associated PhD students have also been excellent drivers of, and ambassadors for, the PG activities.
Expenditure on staff, equipment and consumables is running largely as planned, though the purchase of some equipment items has been delayed.
The original proposal identified a number of milestones within the 4 scientific work packages (SWPs) and 5 technical work packages (TWPs). Some have already been achieved in full, some (as expected) remain work in progress, implementation of a few have been delayed, while other ambitions have emerged (or been moved forward) as a result of new opportunities enabled by the flexibility of the PG. Noteworthy examples in the latter category include the PImMS-driven collaborations with scientists at Aarhus and at DESY (Hamburg), the demonstration of using PImMS sensors in neutron imaging, and computational chemistry collaborations with groups in Munich and in Hokkaido. The possibility of ambient pressure SMI-MS is now being explored with two companies.
The complementarity of many of the PG activities with the ERC funded condensed phase photophysics research programme in Bristol is proving every bit as rewarding as anticipated at the time of the PG submission.
Each lead investigator has sought to make significant contributions in one or more advocacy, leadership and/or outreach areas during the first two years of the PG.
The mid-term review of the PG (Nov 2016) returned the very positive outcome: 5; this is a strong grant that broadly meets all assessment criteria. Following the review, the PG Team produced a set of additional milestones for years 4 and 5, focusing on the development and application of Coulomb-explosion covariance-map imaging methods to explore molecular structure and (photoinduced) dynamics in the gas phase. The team met with the (expanded) External Advisory Board in 9/2017, for which meeting an updated progress report was prepared and circulated. Key advances reported at that time included the successful installation of fsec lasers for Coulomb-explosion imaging studies at both Oxford and Bristol, and many further publications and invited conference presentations describing recent progress in all of the scientific work packages outlined in the original application.
By end of grant (Sept 2019), Coulomb explosion imaging experiments had been established in both Bristol and Oxford, ex PDRA Dr Michael Burt had secured an EPSRC Fellowship to drive future activity in this area in Oxford, many further publications reporting pioneering activities in all areas of the original application (and more) are continuing to appear and all lead investigators continue to be in demand as invited speakers at international conferences in the general area of chemical reaction dynamics.
Exploitation Route Work is ongoing.
Sectors Aerospace, Defence and Marine,Creative Economy,Education,Environment,Healthcare,Manufacturing, including Industrial Biotechology

URL http://dynamics.chem.ox.ac.uk/
 
Description Advised on the RSC's policy on the Plan S open access policy in my capacity as a member of the RSC's Member Communities Board.
Geographic Reach National 
Policy Influence Type Participation in a advisory committee
URL http://www.rsc.org/globalassets/04-campaigning-outreach/policy/research-policy/royal-society-of-chem...
 
Description Chair of Chemistry sub-panel in REF2021
Geographic Reach National 
Policy Influence Type Participation in a national consultation
 
Description Chair of RSC Faraday Division Council
Geographic Reach National 
Policy Influence Type Membership of a guideline committee
URL http://www.rsc.org/Membership/Networking/InterestGroups/FaradayDivision/Council.asp
 
Description Member of Council of Royal Societyl
Geographic Reach National 
Policy Influence Type Membership of a guideline committee
 
Description Member of RSC Faraday Division Council
Geographic Reach National 
Policy Influence Type Membership of a guideline committee
URL http://www.rsc.org/Membership/Networking/InterestGroups/FaradayDivision/Council.asp
 
Description Member of the STFC Physical Sciences and Engineering Adivisor Panel
Geographic Reach National 
Policy Influence Type Participation in a advisory committee
 
Description On behalf of RSC
Geographic Reach National 
Policy Influence Type Membership of a guideline committee
Impact RSC is the learned society for Chemists with a worldwide membership >50000.
URL http://www.rsc.org/about-us/our-structure/#council
 
Description RSC Member Communities Board
Geographic Reach Multiple continents/international 
Policy Influence Type Membership of a guideline committee
Impact Development of RSC's response to Plan S proposals on open-access publishing. Development of RSC's advice on freedom of movement for individuals in the context of Brexit.
 
Description chair of SP8 for REF2021
Geographic Reach National 
Policy Influence Type Participation in a national consultation
 
Description membership of Council of Royal Society
Geographic Reach National 
Policy Influence Type Membership of a guideline committee
Impact Royal Society is premier learned society in UK. Council members advise on RS activities and are the trustees of this charity.
 
Description EPSRC DTP - CASE conversion incentivisation scheme
Amount £73,000 (GBP)
Funding ID D4T00130 
Organisation University of Oxford 
Sector Academic/University
Country United Kingdom
Start 09/2018 
End 09/2022
 
Description EPSRC DTP - CASE conversion incentivisation scheme
Amount £73,000 (GBP)
Funding ID EP/N509711/1 
Organisation University of Oxford 
Sector Academic/University
Country United Kingdom
Start 09/2017 
End 09/2021
 
Description EPSRC Impact Acceleration Account Award
Amount £95,512 (GBP)
Funding ID EP/R511742/1 
Organisation University of Oxford 
Sector Academic/University
Country United Kingdom
Start 09/2018 
End 03/2020
 
Description EU FET-OPEN
Amount € 4,900,000 (EUR)
Funding ID 828753 
Organisation EU-T0 
Sector Public
Country European Union (EU)
Start 01/2019 
End 12/2022
 
Title Data for Norrish calculations 
Description Results from calculations of singlet only contributions to Norrish type I and II reactions. 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
 
Title Inelastic scattering of NO with methane 
Description Velocity map imaging data for the inelastic scattering of NO with methane, using a crossed molecular beam apparatus. 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
 
Title Photodissociation of Methimazole 
Description Results from photodissociation studies on methimazole for the paper "Photofragment Translational Spectroscopy Studies of H Atom Loss Following Ultraviolet Photoexcitation of Methimazole in the Gas Phase" 
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Title Photoinduced C-H bond fission 
Description Perspective on photoinduced C-H bond fission in prototypical organic molecules and radicals 
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Title Quantifying Rival Bond Fission Probabilities following photoexcitation: C-S bond fission in t-butylmethylsulfide 
Description Experimental data sets for the uv photodissociation of t-butylmethylsulfide measured by single photon ionisation coupled to multi-mass VMI. Theoretical calculations of cuts along relevant coordinates of potential energy surfaces and single point vibrational calculations of asymptotic products and parent molecules. 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
 
Description Academic collaborations 
Organisation Aarhus University
Country Denmark 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Complutense University of Madrid
Country Spain 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Dalian Institute of Chemical Physics
Country China 
Sector Private 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Deutsches Electronen-Synchrotron (DESY)
Country Germany 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Hokkaido University
Country Japan 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Johns Hopkins University
Country United States 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Kansas State University
Country United States 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Max Planck Society
Department Fritz Haber Institute
Country Germany 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Moscow State University
Country Russian Federation 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation National Research Council - Ottawa
Country Canada 
Sector Public 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Radboud University Nijmegen
Country Netherlands 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation Sandia Laboratories
Country United States 
Sector Private 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation University of Gothenburg
Country Sweden 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation University of Innsbruck
Country Austria 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation University of Kyoto
Country Japan 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation University of Louisiana at Lafayette
Country United States 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation University of Maryland, College Park
Country United States 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation University of Santiago de Compostela
Country Spain 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Academic collaborations 
Organisation University of Warwick
Department University of Warwick Research Students Skills Programme
Country United Kingdom 
Sector Academic/University 
PI Contribution Numerous scientific collaborations, most of which have already yielded joint publications.
Collaborator Contribution Intellectual input, combining and sharing of knowledge and/or of scientific capability.
Impact See list of outputs
Start Year 2014
 
Description Exploring non-adiabatic coupling in excited state molecules using ultrafast pump-probe laser techniques 
Organisation University of Kyoto
Country Japan 
Sector Academic/University 
PI Contribution PhD student Rebecca Ingle contributed to on-going research in the Suzuki group and acquired new skills and expertise as a result
Collaborator Contribution Prof Suzuki hosted student Rebecca Ingle in his well-equipped laboratory.
Impact One scientific publication, T. Horio, R. Spesyvtsev, K. Nagashima, R. A. Ingle, Y. Suzuki and T. Suzuki, J. Chem. Phys., 2016, 145, 044306.
Start Year 2014
 
Description Microscope mode imaging mass spectrometry 
Organisation Rosalind Franklin Institute
Country United Kingdom 
Sector Charity/Non Profit 
PI Contribution Development of a microscope imaging mass spectrometer using secondary ion mass spectrometry (SIMS), using C60 and water cluster ion guns. This is a collaborative project involving the Rosalind Franklin Institute (RFI) and the company Ionoptika Ltd
Collaborator Contribution The RFI are providing the Phase 1 funding through PDRA support and equipment costs. Ionoptika are providing the C60 ion gun system and water cluster ion gun development, and we are providing the secondary ion time of flight detection capabilities.
Impact None as yet
Start Year 2019
 
Description Oxford-Berlin partnership (with TU, Berlin and FHI, Berlin) "nitrogen oxide reduction at metal centres" 
Organisation Max Planck Society
Department Fritz Haber Institute
Country Germany 
Sector Academic/University 
PI Contribution Expertise, intellectual input, access to unique facilities and instrumentation in a projcet designed to better understand nitrogen oxide reduction at metal centres
Collaborator Contribution Expertise, intellectual input, access to unique facilities and instrumentation
Impact SRM visited Berlin in Febuary 2019 for kick-off meeting and seminar
Start Year 2019
 
Description Oxford-Berlin partnership (with TU, Berlin and FHI, Berlin) "nitrogen oxide reduction at metal centres" 
Organisation Technical University Berlin
Country Germany 
Sector Academic/University 
PI Contribution Expertise, intellectual input, access to unique facilities and instrumentation in a projcet designed to better understand nitrogen oxide reduction at metal centres
Collaborator Contribution Expertise, intellectual input, access to unique facilities and instrumentation
Impact SRM visited Berlin in Febuary 2019 for kick-off meeting and seminar
Start Year 2019
 
Title Molecular Heaters 
Description The invention relates to the use of molecular photon to heat convertors (also known as "molecular heaters") to warm plants, parts of plants or seeds of plants, to methods of using such molecular heaters to warm plants, to plants producing such molecular heaters and to compositions containing such molecular heaters. 
IP Reference GB1715528.4 
Protection Patent application published
Year Protection Granted 2017
Licensed No
Impact N/A
 
Description Oxford Impact short film 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact See url below
Year(s) Of Engagement Activity 2016
URL https://www.youtube.com/watch?v=z6e21GXwnBY&feature=youtu.be
 
Description SUSDG meetings 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Launch of ESR-led Southern Universities Spectroscopy and Dynamics Group series of 2-day meetings (Bristol, Oxford, Nottingham, )
Year(s) Of Engagement Activity 2014
URL http://vallance.chem.ox.ac.uk/SUSDG2015/SUSDG%202015%20Talk%20Titles.pdf