ABSTRACT
We develop an adaptive scheme in the kinetic Monte Carlo simulations, where the adsorption and activation energies of all elementary steps, including the effects of other adsorbates, are evaluated "on-the-fly" by employing the neural network potentials. The configurations and energies evaluated during the simulations are stored for reuse when the same configurations are sampled in a later step. The present scheme is applied to hydrogen adsorption and diffusion on the Pd(111) and Pt(111) surfaces and the CO oxidation reaction on the Pt(111) surface. The effects of interactions between adsorbates, i.e., adsorbate-adsorbate lateral interactions, are examined in detail by comparing the simulations without considering lateral interactions. This study demonstrates the importance of lateral interactions in surface diffusion and reactions and the potential of our scheme for applications in a wide variety of heterogeneous catalytic reactions.
ABSTRACT
The development of new catalysts with high N2 activation ability is an effective approach for low-temperature ammonia synthesis. Herein, we report a novel angstrom-size molybdenum metal cluster catalyst for efficient ammonia synthesis. This catalyst is prepared by the impregnation of a molybdenum halide cluster complex with an octahedral Mo6 metal core on HY zeolite, followed by the removal of all the halide ligands by activation with hydrogen. In this activation, the size of the Mo6 cluster (ca. 7 Å) is almost retained. The resulting angstrom-size cluster shows catalytic activity for ammonia synthesis from N2 and H2, and the reaction proceeds continuously even at 200 °C under 5.0 MPa. DFT calculations suggest that N[triple bond, length as m-dash]N bond cleavage is promoted by the cooperation of the multiple molybdenum sites.
ABSTRACT
For gaining insights into interactions in periodic systems, an analysis is developed based on the fragment molecular orbital method combined with periodic boundary conditions. The adsorption energy is decomposed into guest and surface polarization and deformation energy, guest-surface and guest-guest interactions, and the vibrational free energy. The analysis is applied to the adsorption of guest molecules to Ih (001) ice surface. The cooperativity effects result in a non-linear change in the adsorption energy with coverage due to many-body effects. The role of dispersion is found to be dominant for guests with long hydrophobic tails. A rule is proposed relating the length of the alkyl tail with the formation of the guest layer. The computed binding enthalpies are in good agreement with experimental values. For high coverage, adsorbed molecules can form an ordered layer known as self-assembled monolayer.
ABSTRACT
A fast quantum-mechanical approach, density-functional tight-binding combined with the fragment molecular orbital method and periodic boundary conditions, is used to optimize atomic coordinates and cell parameters for a set of protein crystals: 1ETL, 5OQZ, 3Q8J, 1CBN, and 2VB1. Good agreement between experimental and calculated structures is obtained for both atomic coordinates and cell parameters. Sterical clashes present in the experimental structures are corrected by simulations. The partition analysis is extended to treat periodic boundary conditions and applied to analyze protein-solvent interactions in crystals.