Quantum mechanics orbital properties

Protons are ions—hydrogen atom ions. Why then treat protons apart from other ions The reason is that protons are apart in almost all their physical and chemical characteristics. Consisting solely of the hydrogen atom nucleus with no orbiting electrons, the proton is smaller than the other ions by an effective factor of around 10 -fold. It is an elementary particle of Fermi dimension and can be considered to exhibit properties that lie on the borderline between classical physics and quantum mechanics. Such properties lead to protons having interesting chemical and transport properties. 

The relative size of sodium and potassium ions is an example of a periodic property one that is predictable based on an element s position within the periodic table. In this chapter, we examine several periodic properties of elements, including atomic radius, ionization energy, and electron affinity. We will see that these properties, as well as the overall arrangement of the periodic table, are explained by quantum-mechanical theory, which we examined in Chapter 7. The arrangement of elements in the periodic table— originally based on similarities in the properties of the elements— reflects how electrons fill quantum-mechanical orbitals. 

Unlike quantum mechanics, molecular mechanics does not treat electrons explicitly. Molecular mechanics calculations cannot describe bond formation, bond breaking, or systems in which electron ic delocalization or m oleciilar orbital in teraction s play a m ajor role in determining geometry or properties. 

HyperChem can plot orbital wave functions resulting from semi-empirical and ab initio quantum mechanical calculations. It is interesting to view both the nodal properties and the relative sizes of the wave functions. Orbital wave functions can provide chemical insights. 

In addition to total energy and gradient, HyperChem can use quantum mechanical methods to calculate several other properties. The properties include the dipole moment, total electron density, total spin density, electrostatic potential, heats of formation, orbital energy levels, vibrational normal modes and frequencies, infrared spectrum intensities, and ultraviolet-visible spectrum frequencies and intensities. The HyperChem log file includes energy, gradient, and dipole values, while HIN files store atomic charge values. 

Thermodynamic properties such as heats of reaction and heats of formation can be computed mote rehably by ab initio theory than by semiempirical MO methods (55). However, the Hterature of the method appropriate to the study should be carefully checked before a technique is selected. Finally, the role of computer graphics in evaluating quantum mechanical properties should not be overlooked. As seen in Figures 2—6, significant information can be conveyed with stick models or various surfaces with charge properties mapped onto them. Additionally, information about orbitals, such as the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), which ate important sites of reactivity in electrophilic and nucleophilic reactions, can be plotted readily. Figure 7 shows representations of the HOMO and LUMO, respectively, for the antiulcer dmg Zantac. 

In 1913 Niels Bohr proposed a system of rules that defined a specific set of discrete orbits for the electrons of an atom with a given atomic number. These rules required the electrons to exist only in these orbits, so that they did not radiate energy continuously as in classical electromagnetism. This model was extended first by Sommerfeld and then by Goudsmit and Uhlenbeck. In 1925 Heisenberg, and in 1926 Schrn dinger, proposed a matrix or wave mechanics theory that has developed into quantum mechanics, in which all of these properties are included. In this theory the state of the electron is described by a wave function from which the electron s properties can be deduced. 

Ab initio molecular orbital theory is concerned with predicting the properties of atomic and molecular systems. It is based upon the fundamental laws of quantum mechanics and uses a variety of mathematical transformation and approximation techniques to solve the fundamental equations. This appendix provides an introductory overview of the theory underlying ab initio electronic structure methods. The final section provides a similar overview of the theory underlying Density Functional Theory methods. 

In standard quantum-mechanical molecular structure calculations, we normally work with a set of nuclear-centred atomic orbitals Xi< Xi CTOs are a good choice for the if only because of the ease of integral evaluation. Procedures such as HF-LCAO then express the molecular electronic wavefunction in terms of these basis functions and at first sight the resulting HF-LCAO orbitals are delocalized over regions of molecules. It is often thought desirable to have a simple ab initio method that can correlate with chemical concepts such as bonds, lone pairs and inner shells. A theorem due to Fock (1930) enables one to transform the HF-LCAOs into localized orbitals that often have the desired spatial properties. 

The quantum mechanical description of the Is orbital is similar in many respects to a description of the holes in a much used dartboard. For example, the density of dart holes is constant anywhere on a circle centered about the bullseye, and the "density of dartholes reaches zero only at a very long distance from the bullseye (effectively, at infinity). What are the corresponding properties of a If orbital ... 

In quantum mechanics, angular momenta other than orbital make their appearance. Their structure is not revealed by the simple considerations leading to (7-8). That formula, in fact, arises also from the general transformation properties of vectors under rotation, as will now be shown. 

Chapter I has been reorganized in this edition to give readers a gentler introduction to atoms and their structure. Atoms and molecules, including discussions of quantum mechanics and molecular orbitals, provide the foundation for understanding bulk properties and models of gases, liquids, and solids. 

Because nonmetals do not form monatomic cations, the nature of bonds between atoms of nonmetals puzzled scientists until 1916, when Lewis published his explanation. With brilliant insight, and before anyone knew about quantum mechanics or orbitals, Lewis proposed that a covalent bond is a pair of electrons shared between two atoms (3). The rest of this chapter and the next develop Lewis s vision of the covalent bond. In this chapter, we consider the types, numbers, and properties of bonds that can be formed by sharing pairs of electrons. In Chapter 3, we revisit Lewis s concept and see how to understand it in terms of orbitals. 

Lewis s theory of the chemical bond was brilliant, but it was little more than guesswork inspired by insight. Lewis had no way of knowing why an electron pair was so important for the formation of covalent bonds. Valence-bond theory explained the importance of the electron pair in terms of spin-pairing but it could not explain the properties of some molecules. Molecular orbital theory, which is also based on quantum mechanics and was introduced in the late 1920s by Mul-liken and Hund, has proved to be the most successful theory of the chemical bond it overcomes all the deficiencies of Lewis s theory and is easier to use in calculations than valence-bond theory. 

Molecular properties and reactions are controlled by electrons in the molecules. Electrons had been thonght to be particles. Quantum mechanics showed that electrons have properties not only as particles but also as waves. A chemical theory is required to think abont the wave properties of electrons in molecules. These properties are well represented by orbitals, which contain the amplitude and phase characteristics of waves. This volume is a result of our attempt to establish a theory of chemistry in terms of orbitals — A Chemical Orbital Theory. 

The first (exponential) term represents repulsion between electron orbitals on the atoms. The second term can be seen to be opposite in sign to the first and so represents an attraction—the weak van der Waals interaction between the electron orbitals on approaching atoms. The adjustable parameters can sometimes be calculated using quantum mechanics, but in other systems they are derived empirically by comparing the measured physical properties of a crystal, relative permittivity, elastic constants, and so on, with those calculated with varying parameters until the best fit is obtained. Some parameters obtained in this way, relevant to the calculation of the stability of phases in the system SrO-SrTiC>3, are given in Table 2.3. 

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