Spectroscopy, Structure & Dynamics

Methods for the determination and the prediction of chemical structure and dynamics form the essential foundations of chemistry. This theme offers world-class research in magnetic resonance spectroscopy (both electron paramagnetic resonance and nuclear magnetic resonance), crystallography, theories of fundamental chemical reactions, electronic structure calculation, optical spectroscopy and photon science. Fundamental studies underpin real-world applications; for example research in plasma chemistry has led to the establishment of the startup company Plasma Clean Ltd, while our software for diffusion-ordered NMR spectroscopy is now licensed by one of the world's largest scientific instrument companies. In EPR spectroscopy, the School hosts the EPSRC National EPR Service, providing multi-frequency CW EPR facilities to all UK academic institutions.

Laser spectroscopy (Dr Sven Koehler)

Researchers within the theme hold current grants of over £10M, and have been awarded the Corday-Morgan Medal and Prize, the Tilden Prize (twice) and five other prizes of the Royal Society of Chemistry. Other distinctions include a Sofja Kovalevskaja Award from the Humboldt Foundation, the International EPR Society Young Investigator Medal, the Presidency of the European Crystallographic Association, and the Miller Visiting Professorship of the University of California at Berkeley. Future growth areas include surface dynamics (supported by the nuclear industry, in association with the Dalton Nuclear Institute), the properties and applications of graphene (in collaboration with recent Nobel laureate Konstantin Novoselov), and methods for mixture analysis by NMR and for single molecule spectroscopic studies (supported by EPSRC Advanced Fellowships).

The School of Chemistry has a strong involvement in the Photon Science Institute (PSI), which is directed by Prof Richard Winpenny. The PSI has outstanding facilities for laser studies which are available both to members of the University of Manchester, and to external users where appropriate. A number of academic staff in the School are based in the PSI. Dr Cinzia Casiraghi is collaborating with Professor Novoselov on two projects to investigate the potential applications of graphene as a separation membrane (e.g. for cells, viruses or macromolecules), and as an adaptive focus lens. Dr Steven Magennis is developing single molecule fluorescence techniques. Current areas of application include the investigation of the structure and dynamics of branched DNA and drug-DNA interactions. Resonance-enhanced multi-photon ionization and surface velocity map imaging are being used by Dr Sven Koehler to unravel the dynamics of reactions at surfaces.

Professor Jonathan Connor uses theoretical and computational chemistry to investigate the chemical dynamics of elastic, inelastic and reactive collisions, including, rotational, vibrational and electronic energy transfer. He uses semiclassical approximations, complex angular momentum techniques and nearside-farside theory. Dr Joe McDouall’s research bridges the gap between experimental spectroscopy and quantum mechanics, calculating spectroscopic parameters such as hyperfine couplings, zero field splittings and g tensors in EPR and chemical shifts in NMR, and UV/visible absorption, emission and circular dichroism spectra. Dr Andrew Horn’s work involves the development of novel spectroscopic probes (infrared spectroscopy, mass spectrometry and vibrational sum-frequency spectroscopy) for the study of surfaces and interfaces, in fields ranging from atmospheric science to materials. Crystal structure themes (Prof John Helliwell) include carotenoid binding proteins, protein saccharide recognition, enzyme substrate structures and catalysis, metal aluminophosphates and organic/inorganic structures, and involve development of synchrotron X-ray and neutron facilities. Professor Christopher Whitehead's research looks at the use of plasma discharges for the treatment of waste gas streams; recent work has focused on the synergistic combination of plasma with a catalyst. Optical emission and IR spectroscopy coupled with GC are used to identify the reactive species and products.

The molecular nanomagnetism group of David Collison, Eric McInnes and Richard Winpenny are expert in applying EPR spectroscopy to problems in molecular magnetism. Recent highlights have included the use of EPR spectroscopy to deduce the ground states of high spin molecular nanomagnets, the first report of coherence times measurements in molecular nanomagnets, unravelling the exchange between orbitally degenerate ions, and the use of EPR to measure the weak interactions between molecules that are designed to function as “qubits” for quantum information processing.

With 11 superconducting NMR spectrometers, Manchester Chemistry is a major centre for new NMR techniques. Dr Mathias Nilsson and Prof Gareth Morris have led many of the recent developments in diffusion-ordered spectroscopy (DOSY) and in “pure shift” methods that allow proton NMR spectra to be measured without multiplet structure. NMR spectroscopy is also being used by Dr Louise Natrajan, in conjunction with time-resolved emission spectroscopy, to understand solution structure, speciation and disproportionation mechanisms in actinide complexes. Professor Roy Goodacre uses a range of Raman (micro-)spectroscopies to investigate the structure and behaviour of biological molecules. In particular, UV resonance Raman spectroscopy is a powerful vibrational approach for studying proteins and nucleic acids in solution, and is complementary to Raman conducted in the visible to near IR regions of the EM spectrum.

Recent publications

• Exploiting Non-Innocent Ligands to Prepare Masked Palladium(0) Complexes. DA Smith, AS Batsanov, K Costuas, R Edge, DC Apperley, D Collison, JF Halet, JAK Howard and PW Dyer, Angew. Chem. Int. Ed. 49, 7040-7044 (2010 ).
• Crystallographic Analysis of Counterion Effects on Subtilisin Enzymatic Action in Acetonitrile. M Cianci, B Tomaszewski, JR Helliwell and PJ Halling, J. Am. Chem. Soc. 132, 2293-2300  (2010).
• Kinetic studies of the heterogeneous oxidation of maleic and fumaric acid aerosols by ozone under conditions of high relative humidity. JJ Najera, CJ Percival and AB Horn, Phys. Chem. Chem. Phys. 12, 11417-11427 (2010 ).
• Global Structure of Forked DNA in Solution Revealed by High-Resolution Single-Molecule FRET. T Sabir, GF Schröder, A Toulmin, P McGlynn and SW Magennis, J. Am. Chem. Soc. 133 , 1188-1191  (2011).
• Entanglement in supramolecular spin systems. A Candini, G Lorusso, F Troiani, A Ghirri, S Carretta, P Santini, G Amoretti, C Muryn, F Tuna, G Timco, EJL McInnes, REP Winpenny, W Wernsdorfer and M Affronte, Phys. Rev. Lett. 104, 037203 (2010 ).
• True chemical shift correlation maps: a double pure shift TOCSY experiment. GA Morris, JA Aguilar, R Evans, S Haiber and M Nilsson, J. Am. Chem. Soc. 132, 12770-12772 (2010).
• Dissociation energetics of the phenol⁺ ... Ar₂ cluster ion: The role of π → H isomerization. X Tong, A Armentano, M Riese, M BenYezzar, S Pimblott, K Muller-Dethlefs, S Ishiuchi, M Sakai, A Takeda, M Fujii and O Dopfer, J. Chem. Phys. 133, 154308 (2010).
• Pure Shift Proton NMR: a Resolution of the Resolution Problem?. JA Aguilar, S Faulkner, M Nilsson and GA Morris, Angew. Chem. Int. Ed. 49, 3901-3903 (2010).
• B Ballesteros, TB Faust, C-F Lee, DA Leigh, CA Muryn, RG Pritchard, D Schultz, SJ Teat, GA Timco and REP Winpenny. Synthesis, Structure and Dynamic Properties of Hybrid Organic-Inorganic Rotaxanes. J. Am. Chem. Soc. 132, 15435-15444 (2010).