Chemical elements electronic structure

G. Chemistry of the Transition Elements — Electronic structures, occurrences and recovery, physical and chemical properties of the elements and their compounds, coordination chemistry... 

Porous anodic alumina is a very promising material for nanoelectronics. The injection of different types of impurities inside an alumina matrix can substantially improve its electrophysical properties. It is very important to study the local environment (chemical bonds, electronic structure, etc.) of injected atoms for understanding physical principles of the electronic elements formation. A number of techniques can be used to determine a chemical state of atoms in near surface layers. The most informative and precise technique is X-ray photoelectron spectroscopy. At the same time, Auger electron spectroscopy (AES) is also used for a chemical analysis [1] and can be even applicable for an analysis of dielectrics. The chemical state analysis of Ti and Cu atoms implanted into anodic aliunina films was carried out in this work by means of AES. 

X-ray photoelectron spectroscopy is one of the primary techniques for analyzing the elemental, chemical, and electronic structure of organic materials. For example, it can determine the chemical environment of each of the carbon atoms in a hydrocarbon material. 

The trends in chemical and physical properties of the elements described beautifully in the periodic table and the ability of early spectroscopists to fit atomic line spectra by simple mathematical formulas and to interpret atomic electronic states in terms of empirical quantum numbers provide compelling evidence that some relatively simple framework must exist for understanding the electronic structures of all atoms. The great predictive power of the concept of atomic valence further suggests that molecular electronic structure should be understandable in terms of those of the constituent atoms. 

There are at least four kinds of information available from an Auger spectrum. The simplest and by far most frequently used is qualitative information, indicating which elements are present within the sampling volume of the measurement. Next there is quantitative information, which requires a little more care during acquisition to make it extractable, and a little more effort to extract it, but which tells how much of each of the elements is present. Third, there is chemical information which shows the chemical state in which these elements are present. Last, but by far the least used, there is information on the electronic structure of the material, such as the valance-band density of states that is folded into the line shape of transitions involving valance-band electrons. There are considerations to keep in mind in extracting each of these kinds of information. 

In principle all the X-ray emission methods can give chemical state information from small shifts and line shape changes (cf, XPS and AES in Chapter 5). Though done for molecular studies to derive electronic structure information, this type of work is rarely done for materials analysis. The reasons are the instrumental resolution of commercial systems is not adequate and the emission lines routinely used for elemental analysis are often not those most useftil for chemical shift meas-ure-ments. The latter generally involve shallower levels (narrower natural line widths), meaning longer wavelength (softer) X-ray emission. 

The concept of chemical periodicity is central to the study of inorganic chemistry. No other generalization rivals the periodic table of the elements in its ability to systematize and rationalize known chemical facts or to predict new ones and suggest fruitful areas for further study. Chemical periodicity and the periodic table now find their natural interpretation in the detailed electronic structure of the atom indeed, they played a major role at the turn of the century in elucidating the mysterious phenomena of radioactivity and the quantum effects which led ultimately to Bohr s theory of the hydrogen atom. Because of this central position it is perhaps not surprising that innumerable articles and books have been written on the subject since the seminal papers by Mendeleev in 1869, and some 700 forms of the periodic table (classified into 146 different types or subtypes) have been proposed. A brief historical survey of these developments is summarized in the Panel opposite. 

In so far as the chemical (and physical) properties of an element derive from its electronic configuration, and especially the configuration of its least tightly bound electrons, it follows that chemical periodicity and the form of the periodic table can be elegantly interpreted in terms of electronic structure. 

Organic chemistry, then, is the study of carbon compounds. But why is carbon special Why, of the more than 30 million presently known chemical compounds, do more than 99% of them contain carbon The answers to these questions come from carbon s electronic structure and its consequent position in the periodic table (Figure 1.1). As a group 4A element, carbon can share four valence electrons and form four strong covalent bonds. Furthermore, carbon atoms can bond to one another, forming long chains and rings. Carbon, alone of all elements, is able to form an immense diversity of compounds, from the... 

These correlations between ionization energy and chemical properties confirm the idea that the electronic structure of an element determines its chemical behavior. In particular, the most weakly bound electrons are of greatest importance in this respect. We shall call the electrons that are most loosely bound, the valence electrons. 

In earlier chapters we recognized that strong chemical similarities are displayed by elements which are in the same vertical column of the periodic table. The properties which chlorine holds in common with the other halogens reflect the similarity of the electronic structures of these elements. On the other hand, there is an enormous difference between the behavior of elements on the left side of the periodic table and those on the right. Furthermore, the discussions in Chapter 15 revealed systematic modification... 

The electronic structure of the chlorine atom (3s-3p ) provides a satisfactory explanation of the elemental form of this substance also. The single half-filled 3p orbital can be used to form one covalent bond, and therefore chlorine exists as a diatomic molecule. Finally, in the argon atom all valence orbitals of low energy are occupied by electrons, and the possibility for chemical bonding between the atoms is lost. 

As we saw in Chapter 19, chlorine represents the other extreme in chemical reactivity. Its most obvious chemical characteristic is its ability to acquire electrons to form negative chloride ions, and, in the process, to oxidize some other substance. Since the tendency to lose or gain electrons is a result of the details of the electronic structure of the atom, let us try to explain the chemistry of the third-row elements on this basis. 

We need insight to think like a chemist. Chemical insight means that, when we look at an everyday object or a sample of a chemical, we can imagine the atoms that make it up. Not only that, we need to be able to plunge, in our mind s eye, deep into the center of matter and imagine the internal structure of atoms. To visualize this structure and how it relates to the chemical properties of elements, we need to understand the electronic structure of an atom, the description of how its electrons are arranged around the nucleus. 

The periodic table is one of the most notable achievements in chemistry because it helps to organize what would otherwise be a bewildering array of properties of the elements. However, the fact that its structure corresponds to the electronic structure of atoms was unknown to its discoverers. The periodic table was developed solely from a consideration of physical and chemical properties of the elements. 

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