Chemistry, solid-state origins

Raman spectroscopy failed to live up to its original expectation when the technique was discovered. This was due to instrumental problems, high cost of the instrument, and the fluorescence problem. However, with improvement in instrumentation, the use of a near infrared laser with FT-Raman, the introduction of fiber optics, the number of applications (some of which were discussed in Chapter 3) has escalated. The applications are expanded in this chapter, which deals with materials applications involving structural chemistry, solid state, and surfaces. Additional applications are presented in Chapter 5 (analytical applications), Chapter 6 (biochemical and medical applications) and Chapter 7 (industrial applications). 

Becherescu, D., Cristea, V, Marx, F., Menessy, L, Winter, F. (1983). The Chemistry of Solid State (original in Romanian Chimia Stdrii Solide vol. I) Scientific and Encyclopedic Publishing House (Editura tiin(ifica and Enciclopedica), Bucharest, Vol. L. 

Materials chemistry is now served by a whole range of journals, ranging from the venerable Journal of Solid-State Chemistry and Materials Researeh Bulletin (already mentioned) to Materials Chemistry and Physies (which, interestingly, now incorporates The International Journal of the Chinese Soeiety for Materials Seienee... which appears to be distinct from the Chinese MRS) and Journal of Materials Chemistry (published by the RSC in London) - also Chemistry of Materials, published by the ACS. In France, Annales de Chimie Seienee des Materiaux is an offshoot of a journal originally founded by Lavoisier in 1789 (shortly before he lost his head). Journal of Materials Synthesis and Proeessing is an interesting periodical with somewhat narrower focus. 

Density functional theory was originally developed by solid-state physicists for treating crystalline solids and almost all applications were in that field until the mid-1980s. It is a current hot topic in chemistry, with many papers appearing in the primary journals. 

The development of the method started in the mid 1920 s with the work of Thomas and Fermi [8, 9]. The aim was to formulate an electronic structure theory for the solid state, based on the properties of a homogeneous electron gas, to which we introduce a set of external potentials (i.e. the atomic nuclei). The original formulation, with later additions by Dirac [10] and Slater [11], was, however, inadequate for accurate description of atomic and molecular properties, and it was not until the ground-breaking work of Kohn and coworkers in the mid 1960 s that the theory was put in a form more suited to computational chemistry [12,... 

The exploitation of the reactivity of molecular crystals lies close to the origins of crystal engineering and is at the heart of the pioneering work of Schmidt [47a]. The idea is that of organizing molecules in the solid state using the principles of molecular recognition and self-assembly. Successful results have been obtained with bimolecular reactions, particularly [2+2] photoreactivity and cyclisation [47b,c]. Another important area is that of host-guest chemistry. 

The first explanation and use of such a pseudopotential is due to Heilman5 (1935) who used it in atomic calculations. More recently the pseudopotential concept was reformulated by Phillips and Kleinman7 who were interested in its application to the solid state.8-10 Research in both solid- and liquid-state physics with pseudopotentials was reviewed by Ziman,11 and work in the fields of atomic spectroscopy and scattering has been discussed by Bardsley.12 For an earlier review on applications to the molecular environment the reader is referred to Weeks et a/.13 In this article we shall concentrate on molecular calculations, specifically those of an ab initio nature. Our objective in Section 2 has been to outline the theoretical origins of the pseudopotential approximation, and in Section 3 we have described some of the techniques which have been used in actual calculations. Section 4 attempts to present results from a representative sample of pseudopotential calculations, and our emphasis has been to concentrate on particular molecules which have been the subjects of investigation by the various approaches, rather than to catalogue every available calculation. Finally, in Section 5, we have drawn some conclusions on the relative merits of the different methods and implementations of pseudopotentials. Some of the possible future developments are outlined in the context of the likely progress in quantum chemistry. 

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