Electronic structure basic principles

Computational chemistry has existed for half a century, growing from the province of a small nucleus of theoretical work to a large, significant component of scientific research. By virtue of the great flexibility and power of electronic computers, basic principles of classical and quantum mechanics are now implemented in a form which can handle the many-body problems associated with the structure and behavior of complex molecular systems. The field has reached a stage where the literature is vast and multifaceted. A series of surveys encapsulating major developments, such as those presented in this encyclopedia, is most welcome. 

We shall first review the basic principles of VASP and than describe exemplary applications to alloys and compounds (a) the calculation of the elastic and dynamic properties of a metallic compound (CoSi2), (b) the surface reconstruction of a semiconducting compound (SiC), and (c) the calculation of the structural and electronic properties of K Sbi-j, Zintl-phases in the licpiid state. 

In 1923. Lewis published a classic book (later reprinted by Dover Publications) titled Valence and the Structure of Atoms and Molecules. Here, in Lewis s characteristically lucid style, we find many of the basic principles of covalent bonding discussed in this chapter. Included are electron-dot structures, the octet rule, and the concept of electronegativity. Here too is the Lewis definition of acids and bases (Chapter 15). That same year, Lewis published with Merle Randall a text called Thermodynamics and the Free Energy of Chemical Substances. Today, a revised edition of that text is still used in graduate courses in chemistry. 

In this chapter many of the basic principles related to structure and bonding in molecules have already been illustrated. However, there is another type of compound that is not satisfactorily described by the principles illustrated so far. The simplest molecule of this type is diborane, B2H6. The problem is that there are only 10 valence shell electrons available for use in describing the bonding in this molecule. 

Electron paramagnetic resonance (EPR) and NMR spectroscopy are quite similar in their basic principles and in experimental techniques. They detect different phenomena and thus yield different information. The major use of EPR spectroscopy is in the detection of free radicals which are uniquely characterised by their magnetic moment that arises from the presence of an unpaired electron. Measurement of a magnetic property of a material containing free radicals, like its magnetic susceptibility, provides the concentration of free radicals, but it lacks sensitivity and cannot reveal the structure of the radicals. Electron paramagnetic resonance spectroscopy is essentially free from these defects. 

Here, Flffl are matrix elements of a zeroth-order Hamiltonian, which is chosen as a one-electron operator in the spirit of MP2. is an overlap matrix The excited CFs are not in general orthogonal to each other. Finally, Vf)(i represents the interaction between the excited function and the CAS reference function. The difference between Eq. [2] and ordinary MP2 is the more complicated structure of the matrix elements of the zeroth-order Hamiltonian in MP2 it is a simple sum of orbital energies. Here H is a complex expression involving matrix elements of a generalized Fock operator F combined with up to fourth-order density matrices of the CAS wave function. Additional details are given in the original papers by Andersson and coworkers.17 18 We here mention only the basic principles. The zeroth-order Hamiltonian is written as a sum of projections of F onto the reference function 0)... 

What was the distinction between quantum chemistry and chemical physics After the Journal of Chemical Physics was established, it was easy to say that chemical physics was anything found in the new journal. This included molecular spectroscopy and molecular structures, the quantum mechanical treatment of electronic structure of molecules and crystals and the problem of chemical binding, the kinetics of chemical reactions from the standpoint of basic physical principles, the thermodynamic properties of substances and calculation by statistical mechanical methods, the structure of crystals, and surface phenomena. 

The remarkable variety of redox systems which can already be derived from the Weitz type underline the wide scope of the general structure A and C as a basic principle for two step redox systems. The empirical material as well as general rules regarding structural influences on potentials and Ksem have been developed to such an extent, that redox systems can be taylored to meet special purposes. Catalysts for electron transfer, light positive systems and compounds of high electrical conductivity are some fields in which these redox systems could occupy key positions. Some applications have already been discussed in a previous review of wider scope h)... 

We introduced the basic principles of semiconduction in Section 5.3. Many semiconductors have the cubic sphalerite (zinc blende) structure (Fig. 4.12), which is the same as the diamond lattice (Fig. 3.1) if all the atoms are the same, as in Si or Ge. Inorganic semiconductors generally have four valence electrons per atom, as is the case for Si and Ge. They can be classified according to the number of valence electrons of the participating atoms15 ... 

It has been shown that die BCS theory does lead to die phenomenological equations of London. Pippard and Ginzburg and Landau, and one may therefore state that the basic phenomena of superconductivity are now understood from a microscopic point of view, i.e., in terms of the atomic and electronic structure of solids. It is true, however, that we cannot yet, ub initio, calculate V For a given metal and therefore predict whether it will be superconducting or not. The difficulty here is our ignorance of the exact wave functions to be used in describing the electrons and phonons in a specific metal, and their interactions. However, we believe that the problem is soluble in principle at least. 

Tihe technological properties and the commercial application of several polymer blends have been studied extensively. Investigations of the basic principles, however, relating the phase structure of the blends to the properties of the individual components have not been carried out to an extent justified by the industrial value of these materials. Several methods have been used, the most successful being optical and electron microscopy and dynamic-mechanical measurements. Critical factors and difficulties in the morphological studies of polymer blends have been... 

Following the development of quantum theory by Heisenberg [1] and Schrodinger [2] and a few further discoveries, the basic principles of the structure of atoms and molecules were described around 1930. Unfortunately, the complexity of the Schrodinger equation increases dramatically with the number of electrons involved in a system, and thus for a long time the hydrogen and helium atoms and simple molecules as H2 were the only species whose properties could really be calculated from these first principles. In 1929, Dirac [3] wrote ... 

By exhibiting clearly the basic fact that electrons are wave-like fermions (de Broglie particles that obey the Pauli Exclusion Principle), the LMO-electride ion model of electronic structure enables one to utilize systematically many features of classical physics in developing an understanding , or "explanation , of the properties of quantum mechanical systems. 

Although covalently linked donor-acceptor systems of small organic chromo-phores have been studied for some time in order to uncover the basic principles of electron and energy transfer, the first covalently linked cyclic tetrapyrroles were reported by Gouterman, Dolphin and coworkers in 1972 [27]. In 1976 the first dimeric chlorophyll-based models were reported. Structure la, based upon pyropheophorbide-a, was prepared by Boxer and Closs [28], whereas the pheo-phorbide-a derivative lb was reported by Wasielewski, Studier and Katz [29]. 

Starting from this pioneering work, in the last three decades, a number of researches have developed and used Pearson s principle in order to explore its potentials for studying molecular electronic structure and predicting basic chemical features. 

Resonance was introduced when it was found that there are many molecules whose properties cannot be accounted for by means of a single electronic structure of the VB type, but rather by a combination of several structures [1], Although there is an element of arbitrariness in the resonance theory, in the sense of choosing VB structures, Wheland [50] systemized the basic principles to select the important resonance structures as well as to estimate their relative contribution to the ground state of a molecule. In fact, the qualitative resonance theory enjoyed such a great success due to its convenience and usefulness that resonance has become one of the most fundamental concepts in chemical theory. 

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