Zero-point motion of molecules: beyond Born-Oppenheimer

ORAL

Abstract

We have recently developed a new time-dependent density-functional theory (TDDFT)-based non-Born-Oppenheimer method for computing electron-ion structure of atomistic systems in the path integral formalism. We discuss our implementation of this exact (within the accuracy of DFT) method with a localized basis set approach. The method and the implementation can be used for both molecules and solids. First we apply this method to compute electron-ion states and zero-point energies of small molecules. Next we compare the results of these computations to results obtained from the standard (Born-Oppeheimer-based) path-integral methods used in the field. We demonstrate that at low temperatures the error of the standard path-integral approaches is large even for the systems with wide bandgaps. We discuss potential areas of applicability of our method.

*Army Research Office Multidisciplinary University Research Initiative (MURI), Award No. W911NF-14-0247.

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Presenters

  • Grigory Kolesov

    • School of Engineering and Applied Sciences, Harvard University
    • Physics, Harvard University
    • Department of Physics, Harvard University
    • School of Engineering and Applied Science, Harvard University

Authors

  • Grigory Kolesov

    • School of Engineering and Applied Sciences, Harvard University
    • Physics, Harvard University
    • Department of Physics, Harvard University
    • School of Engineering and Applied Science, Harvard University

  • Efthimios Kaxiras

    • Department of Physics, Harvard University
    • Harvard Univ
    • Harvard University
    • Physics, Harvard University
    • School of Engineering and Applied Science, Harvard University

  • Efstratios Manousakis

    • Florida State Univ
    • Department of Physics and National High Magnetic Field Laboratory, Florida State Unversity
    • National High Magnetic Field Laboratory
    • Physics, Florida State Univ
    • Department of Physics and National High Magnetic Field Laboratory, Florida State University
    • University of Athens, Panepistimioupolis, Zografos, Athens, Greece; Florida State University, Tallahassee, FL, United States; National High Magnetic Field Laboratory