First-principles theoretical studies

Clearly the difficult first principles theoretical study of four-atom reactions, particularly the prototype benchmark H2 + OH <-> H + H2O reaction and its isotopic analogs, has reached as exciting a level as when the first report of... 

The first successful first-principle theoretical studies of the electronic structure of solid surfaces were conducted by Appelbaum and Hamann on Na (1972) and A1 (1973). Within a few years, first-principles calculations for a number of important materials, from nearly free-electron metals to f-band metals and semiconductors, were published, as summarized in the first review article by Appelbaum and Hamann (1976). Extensive reviews of the first-principles calculations for metal surfaces (Inglesfeld, 1982) and semiconductors (Lieske, 1984) are published. A current interest is the reconstruction of surfaces. Because of the refinement of the calculation of total energy of surfaces, tiny differences of the energies of different reconstructions can be assessed accurately. As examples, there are the study of bonding and reconstruction of the W(OOl) surface by Singh and Krakauer (1988), and the study of the surface reconstruction of Ag(llO) by Fu and Ho (1989). 

Tachibana A (2002) First- Principle Theoretical Study on the Dynamical Electronic Characteristics of Electromigration in the Bulk, Surface and Grain Boundary. In Baker SP (ed) Stress Induced Phenomena in Metallization. American Institute of Physics, New York, pp 105-116... 

Very little is known theoretically about the metal-oxide interface although a rather limited number of first principles theoretical studies have dealt with the general problem of metal-ceramic interaction. The aim of this section is to discuss some fundamental aspects of the bonding of metal clusters deposited on the surface of simple binary oxides, in particular MgO and AI2O3. 

Juan Y, Kaxiras E. Generalized stacking fault energy surfaces and dislocation properties of silicon A first-principles theoretical study. Philos. Mag. A 1996 74 1367-1384. 

Zhao K et al (2011) Lithium-assisted plastic deformation of silicon electrodes in lithium-ion batteries a first-principles theoretical study. Nano Lett 11 2962-2967... 

Hod, O., Barone, V., Scuseria, G. E. (2008). Half-metallic graphene nanodots A comprehensive first-principles theoretical study. Physical... 

Mallik BS, Semparithi A, Chandra A (2008) A first principles theoretical study of vibrational spectral diffusion and hydrogen bond dynamics in aqueous ionic solutions D2O in hydration shells of CP ions. J Chem Phys 129 194512... 

An STM image of the two-dimensional Pd O surface oxide is displayed in Fig. 17.12a, together with the proposed atomic structure (Fig. 17.12b) [67]. Studies of oxidized nanoparticles by HRTEM and electron diffraction have reported surface oxides that did not match the structures of bulk oxides (e.g., for Rh [68-70]). With access to advanced imaging methods, such as STM combined with first-principles theoretical modeling using DFT, the exact structure has been determined ([63] and references therein). 

Using the first-principles molecular-dynamics simulation, Munejiri, Shimojo and Hoshino studied the structure of liquid sulfur at 400 K, below the polymerization temperature [79]. They found that some of the Ss ring molecules homolytically open up on excitation of one electron from the HOMO to the LUMO. The chain-like diradicals S " thus generated partly recombine intramolecularly with formation of a branched Sy=S species rather than cyclo-Ss- Furthermore, the authors showed that photo-induced polymerization occurs in liquid sulfur when the Ss chains or Sy=S species are close to each other at their end. The mechanism of polymerization of sulfur remains a challenging problem for further theoretical work. 

Further theoretical studies supported by in situ spectroscopy and high-resolution microscopy are needed to be able to understand this unusually strong bonding between Cu and Ce. To apply such first-principles quantum chemical MD approach, new computational methods accelerating computational time by several orders of magnitude must be developed. 

Recent experimental and theoretical studies on crystal growth, especially in the presence of tailor-made inhibitors, provide a link between macroscopic and microscopic chirality. We shall discuss these principles in some detail for chiral molecules. Furthermore, we shall examine whether it is indeed feasible today to establish the absolute configuration of a chiral crystal from an analysis of solvent-surface interactions. Since these analyses are based on understanding the interactions between a growing crystal and inhibitors present in solution, we shall first illustrate the general mechanism of this effect in various chiral and nonchiral systems. 

There have been a small number of theoretical studies of cation ordering in LDHs. First principles molecular dynamics calculations [43] on [Mg3Al(OH)8]Cl LDHs discussed in Sect. 3.2.6 suggested that structures with adjacent aluminum cations were energetically less favorable than one without, although the chosen arrangement for the latter lacked either hexagonal or rhombohedral supercell. 

Many, if not most, of the perfect surfaces studied by STM have also been studied by first-principles calculations with adequate accuracy. A fast growing field in theoretical surface physics is in first-principles calculations of the surfaces with adsorbates. A recent review of this field in given by Feibelman (1990). As the STM experiments are moving rapidly to the study of adsorbates as well, a direct comparison between the experimental observations and the theoretical predictions becomes practical and desirable. 

The effect of the repulsive atomic force in the STM imaging process is well-established experimentally and theoretically. It is natural to inquire about the effect of the corrugation of attractive forces in the STM imaging process (Wintterlin et al., 1989). The problem was studied using a first-principles numerical method by Ciraci, Baratoff, and Batra (1990a). The major conclusions are as follows ... 

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