Virtual Winter School on Computational Chemistry

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Molecular dynamics

  • Density-Functional Tight-Binding for the Predictive Simulation of Complex Systems

    Speaker: Dr Stephan Irle
    Speaker Link:
    Institute: Oak Ridge National Laboratory
    Country: USA

    Dr Stephan Irle

    Computational Chemistry and Nanomaterials Sciences Group, Computational Sciences and Engineering Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6129, U.S.A.

    The density-functional tight-binding (DFTB) method [1] is an approximation to density functional theory (DFT) allowing a speedup of first principles electronic structure calculations by two to three orders of magnitude.  This is achieved by solving the Kohn-Sham equations for valence electrons using a parameterized two-center Hamiltonian in a minimum pseudoatomic orbital basis set.  Since electronic structure is explicitly computed for each atomic configuration, DFTB is capable of simulating chemical processes including the breaking of covalent bonds, changes in aromatic electronic structure, charge transfer, charge polarization, etc. [2].  DFTB methods can therefore be employed in atomistic molecular dynamics (MD) simulations of processes that involve complex chemical processes, electron transfer, and/or mass and ion transport.  Its applicability is limited in part due to the unfavorable cubic scaling of computer time with system size, and in part due to the necessity of parameterization for element pairs.  Linear-scaling algorithms for massively parallel computation [3,4] and semiautomatic parameterization codes [5] have been developed to address these shortcomings.  Recently, systematic bias corrections were proposed based on a D-machine learning approach employing neural network potentials [6].

    In this talk, I will first briefly review the DFTB method and its various “flavors” for including Coulombic interactions, before highlighting challenges associated with the parameterization of the Hamiltonian.  DFTB-based simulations of nanoscale materials self-assembly will illustrate the predictive power of the method to unravel complex chemical processes occurring in nonequilibrium on large length scales [6].


    Video is available only for registered users.

    pdfPresentation slides


    [1] a) Christensen, A. S.; Kubar, T.; Cui, Q.; Elstner, M. Semiempirical Quantum Mechanical Methods for Noncovalent Interactions for Chemical and Biochemical Applications, Chem. Rev. 2016, 116, 5301-5337; b)

    [2] Cui, Q.; Elstner, M. Density functional tight binding: values of semi-empirical methods in an ab initio era, Phys. Chem. Chem. Phys.2014, 16,14368-14377.

    [3] Nishizawa, H.; Nishimura, Y.; Kobayashi, M.; Irle, S.; Nakai, H. Three pillars for achieving quantum mechanical molecular dynamics simulations of huge systems: Divide-and-conquer, density-functional tight-binding, and massively parallel computation, J. Comp. Chem. 2016, 37, 1983-1992.

    [4] a) Nishimoto, Y.; Fedorov, D. G.; Irle, S. Density-Functional Tight-Binding Combined with the Fragment Molecular Orbital Method, J. Chem. Theory Comput. 2014, 10, 4801-4812; b) Vuong, V. Q.; Nishimoto, Y.; Fedorov, D. G.; Sumpter, B. G.; Niehaus, T. A.; Irle, S. The Fragment Molecular Orbital Method Based on Long-Range Corrected Density-Functional Tight-Binding, J. Chem. Theory Comput. 2019, 15, 3008-3020. 

    [5] Chou, C.-P.; Nishimura, Y.; Fan, C.-C.; Mazur, G.; Irle, S.; Witek, H. A. Automatized Parameterization of DFTB using Particle Swarm Optimization, J. Chem. Theory Comput. 2016, 12, 53-64.

    [6] Zhu, J.; Vuong, V. Q.; Sumpter, B. G.; Irle, S. Artificial Neural Network Correction for Density-Functional Tight-Binding Molecular Dynamics Simulations, MRS Commun. 2019, 9, 867-873 (2019).

    [7] Irle, S; Page, A. J.; Saha, B.; Wang, Y.; Chandrakumar, K. R. S.; Nishimoto, Y.; Qian, H.-J.; Morokuma, K. Atomistic mechanism of carbon nanostructure self-assembly as predicted by nonequilibrium QM/MD simulations, in: J. Leszczynski, M. K. Shukla, Eds. “Practical Aspects of Computational Chemistry II: An Overview of the Last Two Decades and Current Trends”, Springer-European Academy of Sciences, Chapter 5, pp. 105-172 (April 2, 2012).  ISBN 978-94-007-0922-5. DOI: 10.1007/978-94-007-0923-2_5 Preprint:

  • Simulation of association in water: From ion pairing to crystal growth

    Speaker: Professor Julian Gale
    Speaker Link:
    Institute: Curtin University
    Country: Australia

    Professor Julian Gale

    Curtin Institute for Computation/School of Molecular and Life Sciences, Curtin University, PO Box U1987, Perth, WA 6845, Australia

    Many fundamental processes in nature are driven by association of dissolved species in the presence of a solvent, which is typically water. One particularly significant example is biomineralization which is responsible for forming everything from bones and teeth, through to underpinning creation of coral reefs and carbon sequestration. Here dissolved metals ions such as Ca2+ combine with anions such as carbonate and phosphate to ultimate form minerals via a series of complex steps that are still hotly debated [1,2].

    Computational chemistry is able to contribute to our understanding of aqueous binding and crystallization through the potential to quantify the thermodynamics of ion association processes in water, from the initial ion pairing [3] through the surface adsorption of ions that leads to crystal growth [4]. This presentation will focus on some of the computational challenges and pitfalls relating to the quantitative determination of free energies for these association processes in water from molecular dynamics simulation. In particular, the question of how to obtain an accurate potential energy surface will be examined [5], as well as the problem of determining the free energy landscape for complex environments in order to determine meaningful equilibrium constants.


    Video is available only for registered users.


    [1] J.J. De Yoreo et al, Science, 349, 498 (2015)

    [2] D. Gebauer et al, Am. J. Sci., 318, 969 (2018)

    [3] P. Raiteri, R. Demichelis and J.D. Gale, J. Phys. Chem. C, 119, 24447 (2015)

    [4] M. De La Pierre et al, Angewandte Chemie, 56, 8464 (2017)

    [5] P. Raiteri, A. Schuitemaker and J.D. Gale, J. Phys. Chem. B, 124, 3568 (2020)