Combinatorial computational chemistry approach of tight-binding quantum chemical molecular dynamics method to the design of the automotive catalysts

Recently, we have developed a new tight-binding quantum chemical molecular dynamics program “Colors” for combinatorial computational chemistry approach. This methodology is based on our original tight-binding approximation and realized over 5000 times acceleration compared to the conventional first-principles molecular dynamics method. In the present study, we applied our new program to the simulations on various realistic large-scale models of the automotive three-way catalysts, ultrafine Pt particle/CeO₂(111) support. Significant electron transfer from the Pt particle to the CeO₂(111) surface was observed and it was found to strongly depend on the size of the Pt particle. Furthermore, our simulation results suggest that the reduction of the Ce atom due to the electron transfer from the Pt particle to the CeO₂ surface is a main reason for the strong interaction of the Pt particle and CeO₂(111) support.     

Delay of terminal current in systems with abruptly changed Hamiltonian

The current response for the parameter change of a mesoscopic system is a practical issue for future's circuit design. Nowadays most considered cases are various types of bias modulation, while the effect of change of conductor Hamiltonian is seldom addressed. In this paper, we investigate the response of ballistic transport induced by a sudden change of the conductor Hamiltonian. We formulize the terminal current in language of non-equilibrium Green's function. Our method is applied to one-dimensional tight-binding chains and we find that the terminal current has a delay to the Hamiltonian change. The amount of delay is not determined by the velocity of incident electrons in the bias window, but depends on the tight-binding hopping energy γ. The delay of current response at the detecting point away from where the Hamiltonian changes is $C{\gamma }^{?1}$, where C is a constant independent of the system.     

石墨烯能带中的重叠矩阵效应:Tight-Binding方法在模拟中的研究

采用紧束缚方法计算了石墨烯的价带(π)和导带(π*),考虑了非正交基矢下重叠矩阵效应,重叠积分参量s越小,导带越靠近费米面,而价带越远离费米面.在重叠积分参量s≤0.1时,基本保持了原子在实际空间中重叠所引起的能带的改变,太大(s=0.4)则会导致物理上失效.计算了石墨烯的能态密度,在费米面ε=0处(对应Dirac点)的能态密度为零,并且在Dirac点附近呈线性变化.     

A novel graphene nanoribbon field effect transistor with two different gate insulators

In this paper, a novel structure for a dual-gated graphene nanoribbon field-effect transistor (GNRFET) is offered, which combines the advantages of high and low dielectric constants. In the proposed Two Different Insulators GNRFET (TDI-GNRFET), the gate dielectric at the drain side is a material with low dielectric constant to form smaller capacitances, while in the source side, there is a material with high dielectric constant to improve On-current and reduce the leakage current. Simulations are performed based on self-consistent solutions of the Poisson equation coupled with Non-Equilibrium Green's Function (NEGF) formalism in the ballistic regime. We assume a tight-binding Hamiltonian in the mode space representation. The results demonstrate that TDI-GNRFET has lower Off-current, higher On-current and higher transconductance in comparison with conventional low-K GNRFET. Furthermore, using a top-of-the-barrier two-dimensional circuit model, some important circuit parameters are studied. It is found that TDI-GNRFET has smaller capacitances, lower intrinsic delay time and shorter power delay product (PDP) in comparison with high-K GNRFET. Moreover, mobile charge and average velocity are improved in comparison with low dielectric constant GNRFET. The results show that the TDI-GNRFET can provide Drain Induced Barrier Lowering (DIBL) and Subthreshold Swing near their theoretical limits.     

Local electronic and electrical properties of functionalized graphene nano flakes

Based on experimental findings models of amorphous graphene related carbon materials were generated using graphene nano flakes. On the optimized structures detailed local electronic properties were investigated using density functional theory. The electrical conductivities of all these models were also estimated using an in-house program based on tight-binding method. The calculated electrical conductivity values of all the models agreed well with the trend of calculated energy gap and graphitic character.     

Study of reduction processes over cerium oxide surfaces with atomic hydrogen using ultra accelerated quantum chemical molecular dynamics

Ceria plays an important role in catalysis, due to its ability to store and release oxygen depending on the condition present in the catalyst environment. To analyze the role of ceria in catalytic reactions, it is necessary to know the details of the interaction of ceria surface with environmentally sensitive molecules. This study was conducted using ultra accelerated quantum chemical molecular dynamics. Its purpose was to investigate the reduction process of the (1 1 1) and (1 1 0) surfaces of ceria with atomic hydrogen as well as water desorption mechanisms from the surfaces. This simulation demonstrated that when a high-energy colliding hydrogen atoms are adsorbed on the ceria, it pulls up an O atom from the ceria surfaces and results in the formation of a H₂O molecule. This is the first dynamics simulation related to such reduction processes based on quantum chemistry.     

Metastable magnetic configurations of (V, Cr, Mn and Fe) on Ir(0 0 1) surfaces

We present a theoretical study of the electronic and magnetic structure of the 3d-transition metals (M = V, Cr, Mn and Fe) in several overlayer systems. The electronic as well as magnetic structures are investigated for pseudomorphic overlayers (M/Ir(0 0 1)), ordered alloyed overlayers of the type M_0.5Ir_0.5/Ir(0 0 1) and ordered binary surface alloys of V, Cr, Mn and Fe transition metals on Ir(0 0 1) substrates. The calculations are performed with a self-consistent tight-binding method using the unrestricted Hartree-Fock approximation within the Hubbard model. We obtained metastable c(2 × 2) configurations for V, Cr and Mn and a p(1 × 1) configuration for Fe pseudomorphic overlayers. However, ferrimagnetic configuration has been obtained for the ordered surface alloys M_0.5Ir_0.5 and the binary alloyed overlayers on Ir(0 0 1) surfaces.     

Theoretical investigation of encapsulation processes of C60 into single-wall carbon nanotubes

The encapsulation of C₆₀ into single-wall carbon nanotubes is systematically studied by tight-binding molecular dynamics method with an appropriate long-range Lennard-Jones potentials. For a (16,0) nanotube, it is impossible to encapsulate C₆₀ into the tube because of a much larger energy barrier with the relaxation of the open end.