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Homogeneous Catalysis

  • Beyond free energy profiles: Microkinetic modeling and other tricks

    Speaker: Prof. Dr. Feliu Maseras
    Institute: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona
    Country: Spain
    Speaker Link:
    Time: 09:00 CET 29-Jan-24

    Prof. Dr Feliu Maseras

    Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Catalonia, Spain

    Computational chemistry has focused historically in the struggle for the accurate calculation of free energy profiles. Continued progress in computer power and theoretical methods has led in recent years to a situation where these free energy profiles have become rather accurate, in particular in domains such as computational homogeneous catalysis [1]. Because of this, we can now focus on further refinements to bring calculation closer to experiment. One of these refinements is microkinetic modeling, which allows the introduction of the effect of concentrations [2,3].

    feliu pic

    The raw experimental results usually involve reaction times rather than the energy barriers emerging from the free energy profiles. Microkinetic models can make the connection between rate constants calculated from density functional theory (DFT) and reaction times.
    In this presentation we will briefly discuss the idea of the treatment, and present selected examples of application with COPASI, [4] one of the main codes freely available. Other extensions to free energy profiles, such as Marcus theory for single electron transfer steps will be be briefly discussed also.

    Keywords: Density Functional Theory, Microkinetic modeling, Homogeneous catalysis.



    [1] Harvey, J. N.; Himo, F.; Maseras, F.; Perrin, L. ACS Catal. 2019, 9, 6803-6813.
    [2] Besora, M.; Maseras, F. WIREs Comput. Mol. Sci. 2018, 8, e1372.
    [3] Sciortino, G.; Maseras, F. Top Catal. 2022, 65, 105-117.
    [4] (accessed Dec 9 th , 2023).


    Video is available only for registered users.

  • Prediction in organometallic catalysis – a challenge for computational chemistry

    Speaker: Dr Natalie Fey
    Institute: University of Bristol
    Country: UK
    Speaker Link:

    Dr Natalie Fey

    School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS

    Computational studies of homogeneous catalysis play an increasingly important role in furthering (and changing) our understanding of catalytic cycles and can help to guide the discovery and evaluation of new catalysts [1, 2]. While a truly “rational design” process remains out of reach, detailed mechanistic information from both experiment and computation can be combined successfully with suitable parameters characterising catalysts [3] and substrates to predict outcomes and guide screening [4].

    The computational inputs to this process rely on large databases of parameters characterising ligand and complex properties in a range of different environments [5-9]. Such maps of catalyst space can be combined with experimental or calculated response data [7, 9], as well as large-scale data analysis. Rather than pursuing a purely computational solution ofin silico catalyst design and evaluation, an iterative process of mechanistic study, data analysis, prediction and experimentation can accommodate complicated mechanistic manifolds and lead to useful predictions for the discovery and design of suitable catalysts. 

    In this session, I will use examples drawn from our recent work, including the early stages of our development of a reactivity database, to illustrate this approach and discuss why organometallic catalysis is such a challenging yet rewarding area for prediction. 



    1. C. L. McMullin, N. Fey, J. N. Harvey, Dalton Trans., 43 (2014), 13545-13556
    2. N. Fey, M. Garland, J. P. Hopewell, C. L. McMullin, S. Mastroianni, A. G. Orpen, P. G. Pringle, Angew. Chem. Int. Ed., 51 (2012), 118-122.
    3. D. J. Durand, N. Fey, Chem. Rev., 119 (2019), 6561-6594.
    4. J. Jover, N. Fey, Chem. Asian J., 9 (2014), 1714-1723.
    5. A. Lai, J. Clifton, P. L. Diaconescu, N. Fey, Chem. Commun., 55 (2019), 7021-7024.
    6. O. J. S. Pickup, I. Khazal, E. J. Smith, A. C. Whitwood, J. M. Lynam, K. Bolaky, T. C. King, B. W. Rawe, N. Fey, Organometallics, 33 (2014), 1751-1791.
    7. J. Jover, N. Fey, J. N. Harvey, G. C. Lloyd-Jones, A. G. Orpen, G. J. J. Owen-Smith, P. Murray, D. R. J. Hose, R. Osborne, M. Purdie, Organometallics, 29 (2010), 6245-6258.
    8. J. Jover, N. Fey, J. N. Harvey, G. C. Lloyd-Jones, A. G. Orpen, G. J. J. Owen-Smith, P. Murray, D. R. J. Hose, R. Osborne, M. Purdie, Organometallics, 31 (2012), 5302-5306.
    9. A. I. Green, C. P. Tinworth, S. Warriner, A. Nelson, N. Fey, Chem. Eur. J. 2020, Accepted Article, DOI: 10.1002/chem.202003801.