Chemisorption on inverse-supported catalysts: H-ZnO/Ni

The chemisorption energy of hydrogen on a semiconductor/metal composite substrate is investigated using the complex-energy-plane integration approach. The electronic properties of the interfacial substrate are described via a Green-function formalism. The tight-binding approximation is employed to model the semiconductor catalysts by a finite chain of alternating s- and p-orbitals, while the semi-infinite metal support is represented by a linear chain of d-orbitals. Specific calculations are performed for the H-ZnO/Ni system.Dedicated to Professor J. Koutecký on the occasion of his 65th birthdayAlso the Guelph-Waterloo Program for Graduate Work in Physics     

Overlap effects on surface states

A tight-binding investigation is performed of the electronic structure of a semi-infinite monatomic chain, whose atomic orbitals are assumed to be non-orthogonal, so that the effects of overlap can be taken into account. In addition to markedly modifying the bulk band-edges, the presence of overlap also greatly influences the position and existence of the surface states. These latter effects are examined in detail.     

Modified tight-binding equations for electron wave functions in crystals with point defects

A system of tight-binding equations for the electron wave function in infinite, semi-infinite, or interface crystals with point defects is transformed to a finite system for the coefficients of specially constructed converging and diverging waves. The solution of this finite system allows the construction of the electron wave function over all space. This makes it possible to calculate the electronic structure of a defect and its “images” in the various experimental methods used for studying defects in the bulk, on the surface, and at the interface of crystals, without conventional structural simplifications. The proposed method is applied to the calculation of point defects in a two-dimensional square lattice. G. K. Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 6, pp. 985–993, November–December, 1996. Translated by I. Izvekova     

Localized Gaussian type orbital-periodic boundary condition-density functional theory study of infinite-length single-walled carbon nanotubes with various tubular diameters

The detailed geometrical structures of zigzag and armchair type single-walled carbon nanotubes (SWCNTs) with infinite tubular length were investigated using localized Gaussian type orbital-periodic boundary condition-density functional theory (LGTO-PBC-DFT) method. The structures of (n, 0) zigzag SWCNTs were optimized for n = 5-21, (n, n) armchair SWCNTs for n = 3-12. For comparison, the optimized geometry of a two-dimensional graphite sheet was also calculated. It was found that the optimized structures of the SWCNTs showed two C-C bond lengths that decrease with an increase in the tubular diameter. More specifically, the two bond lengths converged with those found in the two-dimensional graphite sheet. We also found a degeneracy in the highest occupied crystal orbitals if identical bond lengths were employed for the zigzag SWCNTs and the two-dimensional graphite sheet. This implies that the two different bond lengths found in the zigzag SWCNTs and the two-dimensional graphite sheet are probably due to the Jahn-Teller effect. The armchair SWCNTs show two slightly different bond lengths if the diameter is less than 12 A; otherwise they are almost identical, approaching the longer bond length of the two-dimensional graphite sheet. This can be due to the fact that the armchair SWCNTs do not have degeneracy in occupied crystal orbitals for identical C-C bond lengths. The crossing point of the conducting and valence bands of each armchair SWCNT were also calculated and show a diameter dependence in which the deviation from 2pi/3a decreases as diameter increases.     

Efficient evaluation of analytic vibrational frequencies in Hartree-Fock and density functional theory for periodic nonconducting systems

We report a method for the efficient evaluation of analytic energy second derivatives with respect to in-phase nuclear coordinate displacements within Hartree-Fock and Kohn-Sham density functional theories using Gaussian orbitals and periodic boundary conditions. The use of an atomic orbital formulation for all computationally challenging steps allows us to adapt the direct space fast multipole method for the Coulomb-type infinite summations. Our implementation also exploits the local character of the exact Hartree-Fock exchange in nonconducting systems. Exchange-correlation contributions are computed using extensive screening and fast numerical quadratures. We benchmark our scheme for in-phase vibrational frequencies of a trans-polyacetylene chain, a two-dimensional boron nitride sheet, and bulk diamond with the 6-31G** basis set and various density functionals. A study of computational scaling with the size of the unit cell for trans-polyacetylene reveals subquadratic scaling for our scheme.     

The role of quantum interference in determining transport properties of molecular bridges

An analytical approach to the electron transport phenomena in molecular devices is presented. The analyzed devices are composed of various molecular bridges attached to two semi-infinite electrodes. Molecular system is described within the tight-binding model, while the coupling to the electrodes is analyzed through the use of Newns-Anderson chemisorption theory. The current-voltage (I-V) characteristics are calculated through the integration of transmission function in the standard Landauer formulation. The essential question of quantum interference effect of electron waves is diseussed in three aspects: (i) the geometry of a molecular bridge, (ii) the presence of an external magnetic field and (iii) the location of chemical substituent.     

Variability in the structures of [4-(aminomethyl)pyridine]silver(I) complexes through effects of ligand ratio, anion, hydrogen bonding, and pi-stacking

The reaction of the asymmetric 4-(aminomethyl)pyridine (4-amp) ligand with silver(I) salts of trifluoromethanesulfonate (triflate, OTf(-)), trifluoroacetate (tfa(-)), or tetrafluoroborate (BF(4)(-)) have produced a variety of one- and two-dimensional structural motifs depending upon the ratio in which the components are mixed. When the proportion of ligand to metal is 1:1, linear coordination polymers are formed with silver(I) OTf(-) (1) and tfa(-) (2). Altering the ratio to 2:1, a linear polymer of corner-shared boxes (3) is formed with tfa(-), a linear box-in-box "chain link" polymer (4) is formed with OTf(-), and a two-dimensional sheet (5) is constructed with BF(4)(-). Addition of 5,5'-dimethyl-2,2'-bipyridine to a solution of 4-ampAgBF(4) disrupts the polymerization of the previous structure and results in the construction of the infinite metal-metal bound strings of 6a regardless of ratio of amp to silver present. H-bonding, pi-stacking, and closed-shell Ag-Ag interactions are all involved in the overall conformations of the final structures.     

Non-steady effective thermal properties of semi-infinite unidirectional fiber-reinforced composites using thermal wave method

Photothermal techniques and effective medium method combining with image method are applied to investigate the non-steady effective thermal properties of semi-infinite unidirectional fiber-reinforced composites, and the effect of the semi-infinite surface on the non-steady effective thermal properties is considered. The dispersion relation for the effective wave number in the semi-infinite random composites is derived. The image method is used to satisfy the adiabatic boundary condition at the semi-infinite surface. The numerical solutions of the non-steady effective thermal properties are obtained by using an iterative scheme. Analyses show that the variation of the non-steady effective thermal properties near the semi-infinite surface is significantly different from those of the infinite composite structure. The effects of the circular frequency of thermal waves, the volume fraction of fibers, and the properties contrast ratio on the maximum non-steady effective properties near the surface are examined. Comparison with the steady case is also given.     

Interactions at the outside faces of calix

Attractive pi-pi interactions between two of the four outside cavity faces of 1,3-bis-pyridylmethylcalix[4]arene (1) and both faces of 1,4-diiodotetrafluorobenzene (2a) form infinite one-dimensional non-covalent ribbons where the two modules alternate. These ribbons are cross-linked by electron donor-acceptor interactions between picolyl nitrogen atoms of calixarene 1 in one chain and iodine atoms of perfluoroarene 2a in another chain and the two-dimensional supramolecular network 3a is formed. A similar behaviour is also shown by 1,4-dibromotetrafluorobenzene (2b). The halogen bonding and the attractive pi-pi interactions occur in directions which are nearly orthogonal each other. Diiodotetrafluorobenzene, being involved in both these interactions, appears to be a particularly interesting tecton. The ability of electron-poor arenes to elicit the exo-receptor potential of calixarene module by connecting their outside faces through pi-pi interactions may be developed as a new and general binding protocol in calixarene self-assembly processes.     

Numerical techniques for investigating an excited state of the anisotropic Heisenberg model

An analysis of the anisotropic Heisenberg model is carried out by solving the Bethe ansatz solution of the model numerically as a function of finite N. A brief introduction to the infinite chain limit is presented and the energy for a few limiting cases of the anisotropy parameter are evaluated. Numerical results for the infinite chain are given which can be compared with the case of finite increasing N. It is shown that the calculation can be extended to the case of an excited state of the model.     

A model of ionic current densities in the vicinity of a corroding disk-shaped region

The scanning vibrating electrode technique (SVET) permits the measurement of ionic corrosion current densities in a uniform electrolyte solution adjacent to an anodic region in a corroding metal sheet. A credible model for such a corrosion experiment envisages a disk-shaped anode embedded in an infinite coplanar sheet of more noble metal, serving as the cathode. If ohmic polarization governs the corrosion rate, then Laplace's equation holds in the steady state. Two independent, but different, solutions of this equation exist, both based on the premise that the two metallic regions have distinct uniform electrical potentials. In this communication, we show these two solutions to be equivalent and thereby predictions are made about the ionic current densities at points in solution near the corrosion site. These predictions are found to be qualitatively similar to reported experimental findings.     

Electronic states of an infinite polyene under local perturbations

A perturbation theory method is developed in the tight-binding LCAO MO treatment of a one-dimensional polymer under local perturbation with the aid of the Wannier function. As the first step, electronic states of an infinite polyene under a few of significant cases of perturbation are formulated in the scheme of the Hückel MO approach, giving the changes in total energies, electron densities, and bond orders of the perturbed systems.     

Electronic Structures of Polymorphic Layers of Borophane

The search for free-standing 2D materials has been one of the most important subjects in the field of studies on 2D materials and their applications. Recently, a free-standing monolayer of hydrogenated boron (HB) sheet has been synthesized by hydrogenation of borophene. The HB sheet is also called borophane, and its application is actively studied in many aspects. Here, we review recent studies on the electronic structures of polymorphic sheets of borophane. A hydrogenated boron sheet with a hexagonal boron frame was shown to have a semimetallic electronic structure by experimental and theoretical analyses. A tight-binding model that reproduces the electronic structure was given and it allows easy estimation of the properties of the material. Hydrogenated boron sheets with more complicated nonsymmorphic boron frames were also analyzed. Using the symmetry restrictions from the nonsymmorphic symmetry and the filling factor of hydrogenated boron sheets, the existence of a Dirac nodal line was suggested. These studies provide basic insights for research on and device applications of hydrogenated boron sheets.     

Small Al clusters on the Cu(111) surface: Atomic relaxation and vibrational properties

The relaxation and vibrational properties of both Al clusters and the (111) surface of a copper sub-strate were studied using the interatomic interaction potentials obtained in a tight-binding approximation. The presence of small aluminum clusters led to modification of the vibrational states of the substrate, a shift of the Rayleigh mode, and excitation of new Z-polarized modes. Hybridized modes localized on the cluster adatoms and the neighboring atoms of the substrate were found in the phonon spectrum. The localized dipole-active modes of the cluster and their strong hybridization with vibrations of the substrate points to desorption stability of the tri- and heptaatomic clusters.     

A CNDO/INDO crystal orbital model for transition metal polymers of the 3d series—basis equations

The crystal orbital formalism in the tight-binding approximation is combined with a recently developed CNDO/INDO model for transition metal species of the 3d series in order to allow band structure calculations on the Hartree-Fock (HF) SCF level for one-dimensional (1D) chains with organometallic unit cells. The band structure approach based on the CNDO and INDO approximation can be used for any atom combination up to bromine under the inclusion of the 3d series. The matrix elements for the tight-binding Hamiltonian are derived for an improved CNDO and INDO framework. The total energy of the 1D chain is partitioned into one-center contributions and into two-center increments of the intracell and intercell type. Semiempirical band structure calculations on simple model systems are compared with available ab initio data of high quality.     

A physical model for the longitudinal polarizabilities of polymer chains

The aim of this work is to provide a physical model to relate the polarizability per unit cell of oligomers to that of their corresponding infinite polymer chains. For this we propose an extrapolation method for the polarizability per unit cell of oligomers by fitting them to a physical model describing the dielectric properties of polymer chains. This physical model is based on the concept of a dielectric needle in which we assume a polymer chain to be well described by a cylindrically shaped nonconducting rod with a radius much smaller than its length. With this model we study in which way the polarizability per unit cell approaches the limit of the infinite chain. We show that within this model the macroscopic contribution of the induced electric field to the macroscopic electric field vanishes in the limit of an infinite polymer chain, i.e., there is no macroscopic screening. The macroscopic electric field becomes equal to the external electric field in this limit. We show that this identification leads to a relation between the polarizability per unit cell and the electric susceptibility of the infinite polymer chain. We test our dielectric needle model on the polarizability per unit cell of oligomers of the hydrogen chain and polyacetylene obtained earlier using time-dependent current-density-functional theory in the adiabatic local-density approximation and with the Vignale-Kohn functional. We also perform calculations using the same theory on truly infinite polymer chains by employing periodic boundary conditions. We show that by extrapolating the oligomer results according to our dielectric needle model we get good agreement with our results from calculations on the corresponding infinite polymer chains.     

Characteristic two-dimensional IR spectroscopic features of antiparallel and parallel beta-sheet polypeptides: simulation studies

The antiparallel and parallel beta sheets are two of the most abundant secondary structures found in proteins. Although various spectroscopic methods have been used to distinguish these two different structures, the linear spectroscopic measurements could not provide incisive information for distinguishing an antiparallel beta sheet from a parallel beta sheet. After carrying out quantum-chemistry calculations and model simulations, we show that the polarization-controlled two-dimensional (2D) IR photon echo spectroscopy can be of critical use in distinguishing these two different beta sheets. Particularly, the ratio between the diagonal peak and the cross peak is found to be strongly dependent on the quasi-2D array of the amide I local-mode transition dipole vectors. The relative intensities of the cross peaks in the 2D difference spectrum of an antiparallel beta sheet are significantly larger than those of the diagonal peaks, whereas the cross-peak amplitudes in the 2D difference spectrum of a parallel beta sheet are much weaker than the main diagonal-peak amplitudes. A detailed discussion on the origin of the diagonal- and cross-peak intensity distributions of both the antiparallel and parallel beta sheets is presented by examining vibrational exciton delocalization, relative angles between two different normal-mode transition dipoles, and natures of the cross peaks in the 2D difference spectrum.     

Energy-transfer and charge-separation pathways in the reaction center of photosystem II revealed by coherent two-dimensional optical spectroscopy

The excited state dynamics and relaxation of electrons and holes in the photosynthetic reaction center of photosystem II are simulated using a two-band tight-binding model. The dissipative exciton and charge carrier motions are calculated using a transport theory, which includes a strong coupling to a harmonic bath with experimentally determined spectral density, and reduces to the Redfield, the F?rster, and the Marcus expressions in the proper parameter regimes. The simulated third order two-dimensional signals, generated in the directions -k(1)+k(2)+k(3), k(1)-k(2)+k(3), and k(1)+k(2)-k(3), clearly reveal the exciton migration and the charge-separation processes.     

Numerical solution for the ground-state energy of the anisotropic Heisenberg model

An analysis of the anisotropic Heisenberg model is carried out by solving the Bethe ansatz solution of the model numerically as a function of the anisotropy parameter for finite N. A brief introduction to the limit of the infinite chain is presented. The energy for a few special limiting cases of the anisotropy parameter in the Hamiltonian are worked out. Numerical results for finite cycles as well as for the infinite chain are given. Comparison can then be made with the case of finite increasing N. © 1997 John Wiley & Sons, Inc.