Atomic orbitals valence-shell electron-pair

The major features of molecular geometry can be predicted on the basis of a quite simple principle—electron-pair repulsion. This principle is the essence of the valence-shell electron-pair repulsion (VSEPR) model, first suggested by N. V. Sidgwick and H. M. Powell in 1940. It was developed and expanded later by R. J. Gillespie and R. S. Nyholm. According to the VSEPR model, the valence electron pairs surrounding an atom repel one another. Consequently, the orbitals containing those electron pairs are oriented to be as far apart as possible. 

Now that we know how to determine hybridization states, we need to know the geometry of each of the three hybridization states. One simple theory explains it all. This theory is called the valence shell electron pair repulsion theory (VSEPR). Stated simply, all orbitals containing electrons in the outermost shell (the valence shell) want to get as far apart from each other as possible. This one simple idea is all you need to predict the geometry around an atom. First, let s apply the theory to the three types of hybridized orbitals. 

The fundamental principle of the Valence-Shell Electron-Pair Repnlsion theory is that the bonding pairs and lone, non-bonding pairs of electrons in the valence level of an atom repel one another. As you know, electron pairs of atoms are localized in orbitals, which are shapes that describe the space in which electrons are most likely to be found around a nucleus. 

The hybridized orbital approach is a simplified way of predicting the geometry of a molecule with three or more atoms by mixing the valence orbitals of its central atom. An alternative approach, valence shell electron-pair repulsion (VSEPR) theory, accomplishes the same thing in a more qualitative way. 

AU acceptable theories should account for the following facts only the heavier, more readily ionizable noble gases form compounds and only the most electronegative atoms or groups are satisfactory hgands for the noble gases. Two theories of bonding in noble gas compounds are discussed here see also Molecular Orbital Theory and Valence Shell Electron Pair Repulsion Model). 

The geometry shown is predicted by VSEPR (valence shell electron pair repulsion) theory, in which orbitals containing valence electrons are directed so that the electrons are as far apart as possible. An asterisk indicates a hybridized atom. 

We now turn from the use of quantum mechanics and its description of the atom to an elementary description of molecules. Although most of the discussion of bonding in this book uses the molecular orbital approach to chemical bonding, simpler methods that provide approximate pictures of the overall shapes and polarities of molecules are also very useful. This chapter provides an overview of Lewis dot structures, valence shell electron pair repulsion (VSEPR), and related topics. The molecular orbital descriptions of some of the same molecules are presented in Chapter 5 and later chapters, but the ideas of this chapter provide a starting point for that more modem treatment. General chemistry texts include discussions of most of these topics this chapter provides a review for those who have not used them recently. 

Valence Shell Electron Pair Repulsion (VSEPR) Theory Hybridization of Atomic Orbitals, sp, sp, sp Single Bonds Conformational Isomers Pi Bonds Pi Barrier to Rotation C/s and Trans, 2p-3p Triple Bonds Cumulenes... 

If the square pyramidal metal carbonyl carbides Fe5(CO)i5C ° and Os5(CO)i5C are treated in a similar manner to I xyi ( ()) i T that is, as clusters in which all four of the core carbon atom s valence shell electrons are used for skeletal bonding, then they are seen to have the expected nido shapes of systems with five skeletal atoms (the metal atoms) held together by seven skeletal bond pairs. By contrast, if these carbide carbon atoms had occupied polyhedral vertex sites, with a lone pair of electrons in an exo-oriented sp hybrid orbital, then the number of skeletal bond pairs would have been reduced by one and the number of skeletal atoms would have increased by one. The five metal atoms and the carbide carbon atom would have had to be accommodated in some way on a trigonal bipyramidal skeleton. Clearly, the assumption that all four valence shell electrons from the carbide carbon atom are involved in the skeletal bonding is vindicated. 

Skill 1.3c-Predict molecular geometries using Lewis dot structures and hybridized atomic orbitals, e.g., valence shell electron pair repulsion model (VSEPR)... 

An important group of cations that shows electronically distorted environments are those of the main group elements in lower oxidation states. These contain nonbonding electron pairs in their valence shells, the so-called lone pairs . Such atoms are usually found displaced from the center of their coordination sphere so as to form between 3 and 5 strong bonds and a number of weaker ones. The effect can be described using the Valence Shell Electron Pair Repulsion (VSEPR) Model [43] in which it is assumed that the cation is surrounded uniformly by between 4 and 7 electron pairs occupying valence shell orbitals. One or more of these is a lone pair... 

Two theories go hand in hand in a discussion of covalent bonding. The valence shell electron pair repulsion (VSEPR) theory helps us to understand and predict the spatial arrangement of atoms in a polyatomic molecule or ion. It does not, however, explain hoav bonding occurs, ] ist where it occurs and where unshared pairs of valence shell electrons are directed. The valence bond (VB) theory describes how the bonding takes place, in terms of overlapping atomic orbitals. In this theory, the atomic orbitals discussed in Chapter 5 are often mixed, or hybridized, to form new orbitals with different spatial orientations. Used together, these two simple ideas enable us to understand the bonding, molecular shapes, and properties of a wide variety of polyatomic molecules and ions. 

In this model the arrangement of bonds around the central atom is considered to depend upon how many valence-shell electron pairs, each occupying a localized one- or two-center orbital, are present, and on the relative sizes and shapes of these orbitals. The first rule is (1) The preferred arrangement of a given number of electron pairs in the valence shell of an atom is that which maximizes their distance apart. 

Organic chemists find that the information obtained from MO theory, where valence electrons occupy bonding and antibonding molecular orbitals, does not always yield the needed information about the bonds in a molecule. The valence-shell electron-pair repulsion (VSEPR) model combines the Lewis concept of shared electron pairs and lone-pair electrons with the concept of atomic orbitals and adds a third principle the minimization of electron repulsion. In this model, atoms share electrons by overlapping... 

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