All Publications


  • Characterizing and Contrasting Structural Proton Transport Mechanisms in Azole Hydrogen Bond Networks Using Ab Initio Molecular Dynamics. The journal of physical chemistry letters Atsango, A. O., Tuckerman, M. E., Markland, T. E. 2021: 8749-8756

    Abstract

    Imidazole and 1,2,3-triazole are promising hydrogen-bonded heterocycles that conduct protons via a structural mechanism and whose derivatives are present in systems ranging from biological proton channels to proton exchange membrane fuel cells. Here, we leverage multiple time-stepping to perform ab initio molecular dynamics of imidazole and 1,2,3-triazole at the nanosecond time scale. We show that despite the close structural similarities of these compounds, their proton diffusion constants vary by over an order of magnitude. Our simulations reveal the reasons for these differences in diffusion constants, which range from the degree of hydrogen-bonded chain linearity to the effect of the central nitrogen atom in 1,2,3-triazole on proton transport. In particular, we uncover evidence of two "blocking" mechanisms in 1,2,3-triazole, where covalent and hydrogen bonds formed by the central nitrogen atom limit the mobility of protons. Our simulations thus provide insights into the origins of the experimentally observed 10-fold difference in proton conductivity.

    View details for DOI 10.1021/acs.jpclett.1c02266

    View details for PubMedID 34478302

  • Interfacial properties of pure and doped CdS/graphene composites: CdS (0001)/graphene and a CdS/graphene bilayer COMPUTATIONAL MATERIALS SCIENCE Bendavid, L., Atsango, A. O., Smith, R. W. 2020; 177
  • Elucidating the Proton Transport Pathways in Liquid Imidazole with First-Principles Molecular Dynamics. The journal of physical chemistry letters Long, Z. n., Atsango, A. O., Napoli, J. A., Markland, T. E., Tuckerman, M. E. 2020: 6156–63

    Abstract

    Imidazole is a promising anhydrous proton conductor with a high conductivity comparable to that of water at a similar temperature relative to its melting point. Previous theoretical studies of the mechanism of proton transport in imidazole have relied either on empirical models or on ab initio trajectories that have been too short to draw significant conclusions. Here, we present the results of multiple time-step ab initio molecular dynamics simulations of an excess proton in liquid imidazole reaching 1 ns in total simulation time. We find that the proton transport is dominated by structural diffusion, with the diffusion constant of the proton defect being ∼8 times higher than that of self-diffusion of the imidazole molecules. By using correlation function analysis, we decompose the mechanism for proton transport into a series of first-order processes and show that the proton transport mechanism occurs over three distinct time and length scales. Although the mechanism at intermediate times is dominated by hopping along pseudo-one-dimensional chains, at longer times the overall rate of diffusion is limited by the re-formation of these chains. These results provide a more complete picture of the traditional idealized Grotthuss structural diffusion mechanism.

    View details for DOI 10.1021/acs.jpclett.0c01744

    View details for PubMedID 32633523