Molecular shape theory

The shape of a molecule determines many of its physical and chemical properties. Often, shapes of reactant molecules determine whether or not they can get close enough to react. Electron densities created by the overlap of the orbitals of shared electrons determine molecular shape. Theories have been developed to explain the overlap of bonding orbitals and can be used to predict the shape of the molecule. 

Another important application of perturbation theory is to molecules with anisotropic interactions. Examples are dipolar hard spheres, in which the anisotropy is due to the polarity of tlie molecule, and liquid crystals in which the anisotropy is due also to the shape of the molecules. The use of an anisotropic reference system is more natural in accounting for molecular shape, but presents difficulties. Hence, we will consider only... 

What Are the Key Ideas The central ideas of this chapter are, first, that electrostatic repulsions between electron pairs determine molecular shapes and, second, that chemical bonds can be discussed in terms of two quantum mechanical theories that describe the distribution of electrons in molecules. 

In this chapter we meet three increasingly sophisticated models of molecular shape. The first considers molecular shape to be a consequence merely of the electrostatic (coulombic) interaction between pairs of electrons. The other two models are theories that describe the distribution of electrons and molecular shape in terms of the occupation of orbitals. 

The Lewis structures encountered in Chapter 2 are two-dimensional representations of the links between atoms—their connectivity—and except in the simplest cases do not depict the arrangement of atoms in space. The valence-shell electron-pair repulsion model (VSEPR model) extends Lewis s theory of bonding to account for molecular shapes by adding rules that account for bond angles. The model starts from the idea that because electrons repel one another, the shapes of simple molecules correspond to arrangements in which pairs of bonding electrons lie as far apart as possible. Specifically ... 

A note on good practice The concepts of promotion, hybridization, and resonance belong to valence bond theory, not molecular orbital theory. Instead, molecular orbitals are built from all the available atomic orbitals by noting whether or not they have the right shape to overlap with one another. 

It is considered that the calculation described in this section agrees well with the experiments for the liquids that have a strong solvation force such as OMCTS and cyclohexane. It may be more difficult to apply this theory to the liquids that have a molecular shape far from spherical and exhibit weak solvation force. 

Existing SEC retention theories have been independently developed for each of the molecular-shape models shown in Figure 1. The deep hollow cyclin-drical pore in the figure (A, B, and C) illustrates the SEC exclusion effect on three types of solute molecules, hard-sphere, rigid-rod, and random-coil, respectively. The individual theories and their bases of commonality are now reviewed briefly. 

Thus, dendrimers exhibit a unique combination of (a) high molecular weights, typical for classical macromolecular substances, (b) molecular shapes, similar to idealized spherical particles and (c) nanoscopic sizes that are larger than those of low molecular weight compounds but smaller than those of typical macromolecules. As such, they provide unique rheological systems that are between typical chain-type polymers and suspensions of spherical particles. Notably, such systems have not been available for rheological study before, nor are there yet analytical theories of dense fluids of spherical particles that are successful in predicting useful numerical results. 

You can use soap bubbles to simulate the molecular shapes that are predicted by VSEPR theory. The soap bubbles represent the electron clouds surrounding the central atom in a molecule. 

Use VSEPR theory to predict the molecular shape for each of the following ... 

Draw Lewis structures for the following molecules and ions, and use VSEPR theory to predict the molecular shape. Indicate the examples in which the central atom has an expanded octet. 

Use VSEPR theory to predict the shape of each of the following molecules. From the molecular shape and the polarity of the bonds, determine whether or not the molecule is polar. 

Q iai f For the compound, GeH4, use VSEPR theory to determine its molecular shape and indicate whether or not this molecule is polar. 

CD If possible for your material, draw a Lewis structure of the molecule or molecules on which your material is based. Predict the molecular shape using VSEPR theory. 

Use VSEPR theory to predict the molecular shape of CH2CI2. Draw a sketch to indicate the polarity of the bonds around the central atom to verify that this is a polar molecule. 

The successful mechanism for a reaction is a theory that correlates the many facts which have been discovered and is fruitful for the prediction of new experiments (1). One approach to mechanism is the study of stereochemistry which seeks information concerning the geometrical relationships between the reactants at the critical stages in the reaction. Information is gleaned from the examination of the products, if several isomers differing only in configuration may be formed, or from a study of the reactivity of closely related substances whose molecular shapes are varied in a specific manner. Occasionally a stereochemical fact places a considerable restraint upon the allowable mechanistic postulates, but the most effective employment of stereochemistry generally depends upon its detailed correlation with other experimental methods. 

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