Bonding, Catalysis, Reactivity and Combustion

Mechanistic studies involve characterising the reactants, transition states (TS), intermediates and products and the energy profiles for transtion from one species to the next. The chemical bonding and charge distribution within these compounds often impacts on the hight of energy barriers to the TS and thus the rate of reaction.

We typically employ DFT and DFT-D methods to determine structures and CCSD(T) to determine energies. MP2 methods are also employed to further recover correlation effects, and compound methods such as ROCBSQB3 are used to obtain very accurate energies for combustion profiles



Research Highlights


  • Nov 2014 Bryan is involved in an article maping the solvent assisted frustriated lewis pair (FLP) clevage of H2
  • June 2013 Dimitris has aced his PhD viva, and has a job in Singapore. Well done! Dimitris computationally studied methyl radical induced decomposition of bio-butanol, and undertook experiments on lamilar flames to understand how bio-fuels behave in combustion engines.
    candle flame flame rig in engine combustion

Publications

  • doi Bypassing a Highly Unstable Frustrated Lewis Pair: Dihydrogen Cleavage by a Thermally Robust Silylium-Phosphine Adduct, T.J. Herrington, B.J. Ward, L.R. Doyle, J. Mcdermott, A.J.P. White, P.A. Hunt and A.E. Ashley, Chem. Comm., 2014 50, p12753
  • doi Thermal decomposition of carboxylate ionic liquids: trends and mechanisms, M. Clough, K. Geyer, P.A. Hunt, J. Mertes and T. Welton, PCCP, 2013, 15, p20480.
  • doi Rate constants of hydrogen abstraction by methyl radical from n-butanol: CanTherm, MultiWell and Variflex compared, D. Katsikadakos, C-W. Zhou,, J.M. Simmie, H.J. Curran, P.A. Hunt, Y. Hardalupas, A.M.K.P. Taylor Proceedings of the Combustion Institute, 2013, Vol:34, Iss 1, p483-491
  • doi Hydrogen Abstraction from n-Butanol by the Methyl Radical: High Level Ab Initio Abstraction Pathways and the Importance of Low Energy Rotational Conformers, Patricia Hunt, Alex Taylor, Yannis Hardalupas and Dimitrios Katsikadakos, PCCP, 2012, 14, 9615-9629
  • doi Understanding siloxane functionalised ionic liquids H. Niedermeyer, M. Ab Rani, P. Lickiss, J. Hallett, T. Welton, A. White and P.A. Hunt, PCCP, 2010, 12 (8), p2018
  • doi Heavier Group 2 Metals and Intermolecular Hydroamination: A Computational and Synthetic Assessment , A. Barrett, C. Brinkmann, M. Crimmin, M. Hill, P. Hunt, P. Procopiou , J. Am. Chem. Soc., 2009, Vol 131, Iss. (36), 12906-12907
  • doi Organolanthanide Mediated Catalytic Cycles: A Computational Perspective, P Hunt, Dalton Transactions, 2007, Vol 18, 1743-54
  • doi Synthesis and characterisation of luminescent fluorinated organoboron compounds., G. Britovsek, J Ugolotti, P. Hunt and A. White, Dalton Trans., 2007, Vol 14, 1425-32
  • doi Lewis and Bronsted multifunctionality: an unusual heterocycle from the reaction of bis(pentafluorophenyl)borinic acid with nitriles., J Ugolotti, S. Hellstrom, G. Britovsek, T. Jones, P. Hunt and A. White, Chem. Com., 2006, Vol 12, 1295-97
  • doi 'Non-Adiabatic Direct Dynamics Study of Chromium Hexacarbonyl Photodissociation' Martin J. Paterson, Patricia A. Hunt, and Michael A. Robb, J. Phys. Chem. A, 2002, 10494.
  • doi Ultrafast Radiationless Deactivation of Organic Dyes: Evidence for a Two-State Two-Mode Pathway in Polymethine Cyanines, A. Sanchez-Galvez, P.A. Hunt, M.A. Robb, M. Olivucci, T. Vreven, and H.B. Schlegel, J. Amer. Chem. Soc., 2000, Vol 122, 2911.
  • doi Relativistic Coupled Cluster Calculations for Neutral and Singly Charged Au3 Clusters, R. Wesendrup, Tricia Hunt, and P. Schwerdtfeger, J. Chem.Phys, 2000, Vol 112, No 21, p9356
  • doi d2 Complexes of Tungsten Containing p-Toluonitrile as a Four- or Two- Electron Donor and Oxidative Addition giving the Two-electron Donor Acylimido Ligand NCOC6H4Me-4, A.J. Nielson, P.A. Hunt, C. Rickard, and P. Schwerdtfeger, J. Chem. Soc., Dalton Trans., 1997, 3311.
  • doi Trends in Inversion Barriers of Group 15 Compounds III. Are Fluorinated Pyridone Derivatives Planar or Nonplanar, P.A. Hunt, P. Schwerdtfeger and T. Fischer, J. Organic Chem., 1997, Vol. 62, Iss. 23, 8063
  • doi Examination of Metal-Silicon Bonding through Structural and Theoretical Studies of an Isostructural Set of Five-Coordinate Silyl Complexes, Os(SiR3)Cl(CO)(PPh3)2 (R = F, Cl, OH, Me), Klaus Hübler, Patricia A. Hunt, Susan M. Maddock, Clifton E. F. Rickard, Warren R. Roper, David M. Salter, Peter Schwerdtfeger, and L. James Wright, Organometallics, 1997, Vol 16 No 23, 5076.
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