Electronic structure impact properties

Section I reviews the new concepts and applications of nanotechnology for catalysis. Chapter 1 provides an overview on how nanotechnology impacts catalyst preparation with more control of active sites, phases, and environment of actives sites. The values of catalysis in advancing development of nanotechnology where catalysts are used to facilitate the production of carbon nanotubes, and catalytic reactions to provide the driving force for motions in nano-machines are also reviewed. Chapter 2 investigates the role of oxide support materials in modifying the electronic stmcture at the surface of a metal, and discusses how metal surface structure and properties influence the reactivity at molecular level. Chapter 3 describes a nanomotor driven by catalysis of chemical reactions. 

Molecular modeling has evolved as a synthesis of techniques from a number of disciplines—organic chemistry, medicinal chemistry, physical chemistry, chemical physics, computer science, mathematics, and statistics. With the development of quantum mechanics (1,2) in the early 1900s, the laws of physics necessary to relate molecular electronic structure to observable properties were defined. In a confluence of related developments, engineering and the national defense both played roles in the development of computing machinery itself in the United States (3). This evolution had a direct impact on computing in chemistry, as the newly developed devices could be applied to problems in chemistry, permitting solutions to problems previously considered intractable. 

In the MO theory, the most reliable approach for the study of reaction pathways perhaps is CASSCF [12, 13], but multi-VBSCF is essentially at the same level with CASSCF [14]. Since a VB wave function can be expanded into the combination of numerous Slater determinants that are used to define configurations in the MO theory, the VB theory provides a very compact, accurate description for chemical reactions. While both MO and VB theories have their own advantages as well as disadvantages, in our opinions, there are some areas where the VB theory is particularly superior to the MO theory 1) the refinement of molecular mechanics force field 2) the development of empirical or semi-empirical VB approaches 3) the impact of intermolecular charge transfer or intramolecular electron delocalization on the structure and properties 4) the validation of classical chemical theories and concepts at the quantitative level 5) the elucidation of chemical reactions and excited states intuitively. 

Several research approaches are pursued in the quest for more efficient and active photocatalysts for water splitting (i) to find new single-phase materials, (ii) to tune the band-gap energy of TJV-active photocatalysts (band-gap engineering), and (iii) to modify the surface of photocatalysts by deposition of cocatalysts to reduce the activation energy for gas evolution. Obviously, the previous strategies must be combined with the control of the s)mthesis of materials to customize the crystallinity, electronic structure, and morphology of materials at nanometric scale, as these properties have a major impact on photoactivity. 

The electronic structure of the imidazolium cations is of interest because it impacts on the hydrogen bond acceptor and donor properties of ionic liquids. This in turn relates to the penchant of the solvent to coordinate to, or react with the solvated species. The imidazolium cation is isoelectronic with the carbene -like imidazole-2-ylidene. Theoretical calculations on deprotonation of the unsubstituted imidazolium cations determine pfCaS of24.90 and 32.97 for the proton at the and C positions... 

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