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Chapter 10: Problem 43

What is molecular orbital theory? How does it differ from valence bond theory?

Short Answer

Expert verified
Molecular Orbital Theory (MOT) presents a molecule as an assembly of nuclei and electrons where electrons move under the influence of the nuclei over the whole molecule, whereas Valence Bond Theory (VBT) suggests that a covalent bond is formed by the overlapping of half-filled atomic orbitals containing electrons with opposite spins. The key difference is that VBT localizes electrons within a bond, while MOT delocalizes them over the entire molecule.

Step by step solution

01

Define Molecular Orbital Theory

Molecular Orbital Theory (MOT) is a method for determining molecular structure in which electrons are not assigned to individual bonds between atoms, but are treated as moving under the influence of the nuclei in the whole molecule.
02

Key Features of Molecular Orbital Theory

The key assumptions of MOT are: \n1. The electrons in a molecule are present in the various molecular orbitals.\n2. These molecular orbitals are formed as a result of the linear combination of atomic orbitals.\n3. Molecular orbitals, once formed, are spread over the entire molecule i.e., they are delocalized.\n4. Molecular orbitals can accommodate a maximum of two electrons, have opposite spins and follow Pauli's Exclusion Principle.
03

Define Valence Bond Theory

Valence Bond Theory (VBT), on the other hand, explains the formation of covalent bond quantitatively using quantum mechanics. Electrons are assumed to localize between the two bonding atoms.
04

Key Features of Valence Bond Theory

Some main features of this theory are: \n1. A covalent bond is formed by the overlapping of half-filled atomic orbitals of two atoms.\n2. The orbitals that overlap must have the same energy.\n3. The two electrons forming a covalent bond must spin in opposite directions.\n4. The overlap of orbitals with one electron each results in a maximum of two electrons in the molecular orbitals forming a covalent bond.
05

Contrast Between Molecular Orbital Theory and Valence Bond Theory

The primary difference between these two theories is the approach to the electronic structure of molecules. VBT localizes electrons in a bond between two atoms, while MOT delocalizes the electrons over the entire molecule. The other significant difference is that VBT can't explain the color and magnetic properties of coordination compounds as adequately as MOT. Furthermore, MOT also explains the stability of molecules.

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Most popular questions from this chapter

The molecules cis-dichloroethylene and transdichloroethylene shown on p. 324 can be interconverted by heating or irradiation. (a) Starting with cis-dichloroethylene, show that rotating the \(\mathrm{C}=\mathrm{C}\) bond by \(180^{\circ}\) will break only the pi bond but will leave the sigma bond intact. Explain the formation of trans- dichloroethylene from this process. (Treat the rotation as two, stepwise \(90^{\circ}\) rotations.) (b) Account for the difference in the bond enthalpies for the pi bond (about \(270 \mathrm{~kJ} / \mathrm{mol}\) ) and the sigma bond (about \(350 \mathrm{~kJ} / \mathrm{mol}\) ). (c) Calculate the longest wavelength of light needed to bring about this conversion.

Consider a \(\mathrm{N}_{2}\) molecule in its first excited electronic state; that is, when an electron in the highest occupied molecular orbital is promoted to the lowest empty molecular obital. (a) Identify the molecular orbitals involved and sketch a diagram to show the transition. (b) Compare the bond order and bond length of \(\mathrm{N}_{2}{ }^{*}\) with \(\mathrm{N}_{2}\), where the asterisk denotes the excited molecule. (c) Is \(\mathrm{N}_{2}{ }^{*}\) diamagnetic or paramagnetic? (d) When \(\mathrm{N}_{2} *\) loses its excess energy and converts to the ground state \(\mathrm{N}_{2}\), it emits a photon of wavelength \(470 \mathrm{nm}\), which makes up part of the auroras lights. Calculate the energy difference between these levels.

Use valence bond theory to explain the bonding in \(\mathrm{Cl}_{2}\) and \(\mathrm{HCl}\). Show how the atomic orbitals overlap when a bond is formed

The allene molecule \(\mathrm{H}_{2} \mathrm{C}=\mathrm{C}=\mathrm{CH}_{2}\) is linear (the three \(\mathrm{C}\) atoms lie on a straight line). What are the hybridization states of the carbon atoms? Draw diagrams to show the formation of sigma bonds and pi bonds in allene.

Explain why an atom cannot have a permanent dipole moment.
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