Tetsuya Morishita

Effects of Oxygen Adsorption on the Surface State of Epitaxial Silicene on Ag(111)

Epitaxial silicene, which is one single layer of silicon atoms packed in a honeycomb structure, demonstrates a strong interaction with the substrate that dramatically affects its electronic structure. The role of electronic coupling in the chemical reactivity between the silicene and the substrate is still unclear so far, which is of great importance for functionalization of silicene layers. Here, we report the reconstructions and hybridized electronic structures of epitaxial 4 × 4 silicene on Ag(111), which are revealed by scanning tunneling microscopy and angle-resolved photoemission spectroscopy. The hybridization between Si and Ag results in a metallic surface state, which can gradually decay due to oxygen adsorption. X-ray photoemission spectroscopy confirms the decoupling of Si-Ag bonds after oxygen treatment as well as the relatively oxygen resistance of Ag(111) surface, in contrast to 4 × 4 silicene [with respect to Ag(111)]. First-principles calculations have confirmed the evolution of the electronic structure of silicene during oxidation. It has been verified experimentally and theoretically that the high chemical activity of 4 × 4 silicene is attributable to the Si pz state, while the Ag(111) substrate exhibits relatively inert chemical behavior.

Monolayer-to-bilayer transformation of silicenes and their structural analysis

Silicene, a two-dimensional honeycomb network of silicon atoms like graphene, holds great potential as a key material in the next generation of electronics; however, its use in more demanding applications is prevented because of its instability under ambient conditions. Here we report three types of bilayer silicenes that form after treating calcium-intercalated monolayer silicene (CaSi2) with a BF4− -based ionic liquid. The bilayer silicenes that are obtained are sandwiched between planar crystals of CaF2 and/or CaSi2, with one of the bilayer silicenes being a new allotrope of silicon, containing four-, five- and six-membered sp3 silicon rings. The number of unsaturated silicon bonds in the structure is reduced compared with monolayer silicene. Additionally, the bandgap opens to 1.08 eV and is indirect; this is in contrast to monolayer silicene which is a zero-gap semiconductor.

Molecular dynamics simulations of self-organized polyicosahedral Si nanowire

A novel polyicosahedral nanowire is spontaneously formed in a series of annealing molecular dynamics simulations of liquid Si inside a nanopore of 1.36 nm in diameter. The polyicosahedral Si nanowire is stable even in a vacuum up to about 77% of the melting temperature of bulk Si. Our structural energy calculations reveal that the polyicosahedral nanowire is energetically advantageous over the pentagonal one for a wire whose diameter is less than 6.02 nm, though the latter has been recently proposed as the lowest energy wire. These results suggest the possibility of the formation of a new stable polyicosahedral Si nanowire.

Enhanced sampling via strong coupling to a heat bath: Relationship between Tsallis and multicanonical algorithms

We show that Tsallis and multicanonical statistical mechanics are equivalent under specific conditions and that they describe a system strongly coupled to a heat bath. The concept of the strong coupling to a heat bath, in which energy fluctuation is larger than that in the canonical ensemble [J. Chem. Phys. 119, 7075 (2003)], plays a key role in relating Tsallis formalism to multicanonical formalism. The equivalence between these formalisms allows us to obtain an appropriate q parameter in the Tsallis algorithm to enhance the sampling in the phase space in a manner similar to the multicanonical algorithm. An enhanced sampling in the configurational space by use of the strong coupling formalism is demonstrated in a Lennard-Jones fluid.

Does supercooled liquid Si have a density maximum

We have performed precise measurements of the density of supercooled liquid silicon (l-Si) in the temperature range of 1530-1800 K using an electromagnetic levitation (EML) technique with static magnetic fields. We also performed first-principles molecular dynamics simulation (FPMD) of supercooled l-Si. The observed density of the supercooled l-Si and the FPMD results show good agreement in the temperature range of 1530-1800 K. The structure of the supercooled l-Si also showed good agreement between the experimental measurements and FPMD simulations. Based on these results, we discuss nucleation in supercooled l-Si and also the existence of a density maximum in the supercooled l-Si, which is well known in water at 4 degrees C.

Anion secondary batteries utilizing a reversible BF4 insertion/extraction two-dimensional Si material

The development of lightweight, long lasting Li-ion batteries is of great technological importance for hybrid and plug-in hybrid electric vehicles, as well as for power grid applications. Here we report an alternative approach to the use of Li cations, based on the fabrication of BF4 anion rocking-chair-type secondary batteries. For the anode material, we report a Si-based compound, [Si10H8(OCH2CH2NH(CH3)2)2](BF4)2, which is capable of reacting with two BF4 anions per formula unit at a potential of 1.8 V, giving a reversible capacity of 80mA h g−1. This anion battery also showed superior performance under thermal abuse compared with Li-ion batteries. Furthermore, the anion battery is operable at −30 °C, a temperature at which Li-ion batteries are generally not operable because Li-ions are solvated by coordination with basic organic molecules around this temperature.

Extended Phase-Space Methods for Enhanced Sampling in Molecular Simulations: A Review

Molecular Dynamics simulations are a powerful approach to study biomolecular conformational changes or protein–ligand, protein–protein, and protein–DNA/RNA interactions. Straightforward applications, however, are often hampered by incomplete sampling, since in a typical simulated trajectory the system will spend most of its time trapped by high energy barriers in restricted regions of the configuration space. Over the years, several techniques have been designed to overcome this problem and enhance space sampling. Here, we review a class of methods that rely on the idea of extending the set of dynamical variables of the system by adding extra ones associated to functions describing the process under study. In particular, we illustrate the Temperature Accelerated Molecular Dynamics (TAMD), Logarithmic Mean Force Dynamics (LogMFD), and Multiscale Enhanced Sampling (MSES) algorithms. We also discuss combinations with techniques for searching reaction paths. We show the advantages presented by this approach and how it allows to quickly sample important regions of the free-energy landscape via automatic exploration.

Structural, electronic, and vibrational properties of high-density amorphous silicon: A first-principles molecular-dynamics study

We report a first-principles study of the structural, electronic, and dynamical properties of high-density amorphous (HDA) silicon, which was found to be formed by pressurizing low-density amorphous (LDA) silicon (a normal amorphous Si) [T. Morishita, Phys. Rev. Lett. 93, 055503 (2004); P. F. McMillan, M. Wilson, D. Daisenberger, and D. Machon, Nature Mater. 4, 680 (2005)]. Striking structural differences between HDA and LDA are revealed. The LDA structure holds a tetrahedral network, while the HDA structure contains a highly distorted tetrahedral network. The fifth neighboring atom in HDA tends to be located at an interstitial position of a distorted tetrahedron composed of the first four neighboring atoms. Consequently, the coordination number of HDA is calculated to be approximately 5 unlike that of LDA. The electronic density of state (EDOS) shows that HDA is metallic, which is consistent with a recent experimental measurement of the electronic resistance of HDA Si. We find from local EDOS that highly distorted tetrahedral configurations enhance the metallic nature of HDA. The vibrational density of state (VDOS) also reflects the structural differences between HDA and LDA. Some of the characteristic vibrational modes of LDA are dematerialized in HDA, indicating the degradation of covalent bonds. The overall profile of the VDOS for HDA is found to be an intermediate between that for LDA and liquid Si under pressure (high-density liquid Si).

How silicene on Ag(111) oxidizes: Microscopic mechanism of the reaction of O2 with silicene

We demonstrate, using first-principles molecular-dynamics simulations, that oxidation of silicene can easily take place either at low or high oxygen doses, which importantly helps clarify previous inconsistent reports on the oxidation of silicene on the Ag(111) substrate. We show that, while the energy barrier for an O2 molecule reacting with a Si atom strongly depends on the position and orientation of the molecule, the O2 molecule immediately dissociates and forms an Si-O-Si configuration once it finds a barrier-less chemisorption pathway around an outer Si atom of the silicene overlayer. A synergistic effect between the molecular dissociation and subsequent structural rearrangements is found to accelerate the oxidation process at a high oxygen dose. This effect also enhances self-organized formation of sp3-like tetrahedral configurations (consisting of Si and O atoms), which results in collapse of the two-dimensional silicene structure and its exfoliation from the substrate. We also find that the electronic properties of the silicene can be significantly altered by oxidation. The present findings suggest that low flux and low temperature of the oxygen gas are key to controlling oxidation of silicene.

From Nosé–Hoover chain to Nosé–Hoover network: design of non-Hamiltonian equations of motion for molecular-dynamics with multiple thermostats

A systematic algorithm to design multiple thermostat systems in the framework of the Nosé–Hoover type non-Hamiltonian formulation is presented. Using ‘non uniform’ time transformations in a generalised Hamiltonian equation, we develop the non-Hamiltonian equations of motion for multiple thermostat systems having an arbitrary number of thermostats and arbitrary connections between a physical system and thermostats (‘Nosé–Hoover network’). We then present the algorithm to construct the Nosé–Hoover network equations based on a simple diagram only. On the basis of this algorithm, recursively attached Nosé–Hoover thermostats are introduced as an example of the Nosé–Hoover network and its high efficiency in sampling the canonical distribution for an one-dimensional double-well system is illustrated by numerical calculations.