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Ch.9 - Molecular Geometry and Bonding Theories
Chapter 9, Problem 109b

The energy-level diagram in Figure 9.40 shows that the sideways overlap of a pair of p orbitals produces two molecular orbitals, one bonding and one antibonding. In ethylene there is a pair of electrons in the bonding orbital between the two carbons. Absorption of a photon of the appropriate wavelength can result in promotion of one of the bonding electrons from the to the molecular orbital. b. Assuming this electronic transition corresponds to the HOMO–LUMO transition, what is the LUMO in ethylene?

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Molecular Orbitals

Molecular orbitals (MOs) are formed from the linear combination of atomic orbitals (LCAO) when atoms bond. In ethylene, the sideways overlap of p orbitals creates two types of MOs: bonding and antibonding. The bonding molecular orbital is lower in energy and stabilizes the molecule, while the antibonding orbital is higher in energy and destabilizes it. Understanding these orbitals is crucial for analyzing electronic transitions in molecules.
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HOMO and LUMO

The Highest Occupied Molecular Orbital (HOMO) is the molecular orbital that contains the highest energy electrons in a molecule, while the Lowest Unoccupied Molecular Orbital (LUMO) is the lowest energy orbital that is unoccupied. In ethylene, the transition of an electron from the HOMO to the LUMO upon photon absorption is fundamental to understanding its electronic properties and reactivity. Identifying these orbitals helps predict how the molecule will interact with light.

Electronic Transitions

Electronic transitions refer to the movement of electrons between different energy levels or orbitals within a molecule, typically induced by the absorption of light. In the context of ethylene, when a photon of the appropriate wavelength is absorbed, an electron can be promoted from the bonding orbital (HOMO) to the antibonding orbital (LUMO). This transition is essential for understanding the absorption spectrum and the photochemical behavior of the molecule.
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Related Practice
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Azo dyes are organic dyes that are used for many applications, such as the coloring of fabrics. Many azo dyes are derivatives of the organic substance azobenzene, C12H10N2. A closely related substance is hydrazobenzene, C12H12N2. The Lewis structures of these two substances are

(Recall the shorthand notation used for benzene.) (c) Predict the N¬N¬C angles in each of the substances.

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Textbook Question

Carbon monoxide, CO, is isoelectronic to N2. (d) Would you expect the p2p MOs of CO to have equal atomic orbital contributions from the C and O atoms? If not, which atom would have the greater contribution?

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Textbook Question

The energy-level diagram in Figure 9.40 shows that the sideways overlap of a pair of p orbitals produces two molecular orbitals, one bonding and one antibonding. In ethylene there is a pair of electrons in the bonding orbital between the two carbons. Absorption of a photon of the appropriate wavelength can result in promotion of one of the bonding electrons from the to the molecular orbital. a. Assuming this electronic transition corresponds to the HOMO–LUMO transition, what is the HOMO in ethylene?

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Textbook Question

The energy-level diagram in Figure 9.40 shows that the sideways overlap of a pair of p orbitals produces two molecular orbitals, one bonding and one antibonding. In ethylene there is a pair of electrons in the bonding orbital between the two carbons. Absorption of a photon of the appropriate wavelength can result in promotion of one of the bonding electrons from the to the molecular orbital. c. Is the bond in ethylene stronger or weaker in the excited state than in the ground state? Why?

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Textbook Question

Sulfur tetrafluoride 1SF42 reacts slowly with O2 to form sulfur tetrafluoride monoxide 1OSF42 according to the following unbalanced reaction: SF41g2 + O21g2¡OSF41g2 The O atom and the four F atoms in OSF4 are bonded to a central S atom. (a) Balance the equation.

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Textbook Question

Sulfur tetrafluoride (SF4) reacts slowly with O2 to form sulfur tetrafluoride monoxide (OSF4) according to the following unbalanced reaction: SF4(g) + O2(g) → OSF4(g) The O atom and the four F atoms in OSF4 are bonded to a central S atom. (b) Write a Lewis structure of OSF4 in which the formal charges of all atoms are zero.

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