Molecular geometry prediction

In Chapter 7, we used valence bond theory to explain bonding in molecules. It accounts, at least qualitatively, for the stability of the covalent bond in terms of the overlap of atomic orbitals. By invoking hybridization, valence bond theory can account for the molecular geometries predicted by electron-pair repulsion. Where Lewis structures are inadequate, as in S02, the concept of resonance allows us to explain the observed properties. 

One effect of the greater flexibility inherent in the INDO scheme is that valence bond angles are predicted with much greater accuracy than is the case for CNDO. Nevertheless, overall molecular geometries predicted from INDO tend to be rather poor. However, if a good molecular geometry is available from some other source (ideally experiment) the INDO method has considerable potential for modeling the UV/Vis spectroscopy of the compound because of its better treatment of one-center electronic interactions. 

THE ACCURACY OF MOLECULAR GEOMETRY PREDICTIONS BY QUANTUM CHEMICAL METHODS... 

As we examine the common types of hybridization, notice the connection between the type of hybridization and certain of the molecular geometries predicted by the VSEPR model linear, bent, trigonal planar, and tetrahedral. 

The molecules S1F4, SF4, and Xep4 have molecular formulas of the type AF4, but the molecules have different molecular geometries. Predict the shape of each molecule, and explain why the shapes differ. 

I>raw the Lewis structure for the 803 ion. What is the electron-domain geometry What is the molecular geometry Predict the ideal O—S—O bond angle. What hybrid orbitals does S use in bonding ... 

Questions 19 through 30 For each molecule or ion, or for the atom specified in a molecule or ion, write the Lewis diagram, then describe (a) the electron-pair geometry and (b) the molecular geometry predicted by the valence shell electron-pair repulsion theory. Also sketch the three-dimensional ball-and-stick representation of each molecule or ion in Questions 19-22. 

The primary reason for interest in extended Huckel today is because the method is general enough to use for all the elements in the periodic table. This is not an extremely accurate or sophisticated method however, it is still used for inorganic modeling due to the scarcity of full periodic table methods with reasonable CPU time requirements. Another current use is for computing band structures, which are extremely computation-intensive calculations. Because of this, extended Huckel is often the method of choice for band structure calculations. It is also a very convenient way to view orbital symmetry. It is known to be fairly poor at predicting molecular geometries. 

Practically all CNDO calculations are actually performed using the CNDO/ 2 method, which is an improved parameterization over the original CNDO/1 method. There is a CNDO/S method that is parameterized to reproduce electronic spectra. The CNDO/S method does yield improved prediction of excitation energies, but at the expense of the poorer prediction of molecular geometry. There have also been extensions of the CNDO/2 method to include elements with occupied d orbitals. These techniques have not seen widespread use due to the limited accuracy of results. 

Extended Hiickel gives a qualitative view of the valence orbitals. The formulation of extended Hiickel is such that it is only applicable to the valence orbitals. The method reproduces the correct symmetry properties for the valence orbitals. Energetics, such as band gaps, are sometimes reasonable and other times reproduce trends better than absolute values. Extended Hiickel tends to be more useful for examining orbital symmetry and energy than for predicting molecular geometries. It is the method of choice for many band structure calculations due to the very computation-intensive nature of those calculations. 

We can combine our knowledge of molecular geometry with a feel for the polarity of chemical bonds to predict whether a molecule has a dipole moment or not The molec ular dipole moment is the resultant of all of the individual bond dipole moments of a substance Some molecules such as carbon dioxide have polar bonds but lack a dipole moment because their geometry causes the individual C=0 bond dipoles to cancel... 

Although reservations have been expressed concerning VSEPR as an explanation for molecular geometries, it remains a useful tool for predicting the shapes of organic compounds. 

CNDO/2 for predicting molecular geometries, it gave a vastly superior treatment of singlet-triplet splittings and spin densities. 

It became apparent that these STO-hG minimal basis sets were not particularly adequate for the accurate prediction of molecular geometries, and this failing was attributed to their lack of flexibility in the valence region. The next step was to give a little more flexibility to the STO- Gbasis sets, whilst retaining their computational attractiveness. The classic paper is that by Ditchfield, Hehre and Pople. 

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. 

Use Table 7.3 and Figure 7.8, applying the VSEPR, to predict molecular geometry. 

VSEPR model Valence Shell Electron Pair Repulsion model, used to predict molecular geometry states that electron pairs around a central atom tend to be as far apart as possible, 180-182... 

C09-0129. Tellurium compounds, which are toxic and have a hideous stench, must be handled with extreme care. Predict the formula of the tellurium-fluorine molecule or ion that has the following molecular geometry (a) bent (b) T-shaped (c) square pyramid (d) trigonal bipyramid (e) octahedron and (Q seesaw. 

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