Lecture+24_MO+Theory+Heteronuclear+Diatomics_Practice+Problems

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Oct 30, 2023

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Announcements for October 27 th , 2023 Homework 8 due Sunday, October 29 th , 11:59 PM Quiz 8 is available this weekend from Saturday to Sunday @ 5pm Recitation 7 is tomorrow Exam 2 is scheduled for Monday, October 30 th 7:00 9:00 pm Covers Lectures 11 24 (MO Theory is final topic) Note sheet for exam: 1 page, front and back, HANDWRITTEN ONLY (on paper in pen or pencil)!!! No typing, no computer-generated figures. Review Session is Sunday, October 29 th from 4 pm 6 pm in Chem 102 with Taehwan This Week Reading: Chapter 9, Sections 7 8 Monday Reading: Chapter 23, Sections 1 3 and 5 6 Wednesday Reading: Chapter 23, Sections 5 6 and Chapter 3, Section 3 Friday Reading: Chapter 3, Sections 1, 2, 5, and 6 Our objective is to explore a 2 nd approach to describe chemical covalent bonding The plan: MO Theory HX molecules Practice Problems π systems and delocalization
Consider the heteronuclear diatomic molecule, [BO] - . Use MO theory (z-axis is the bonding axis) to predict the [BO] - bond order and sketch the HOMO and LUMO . Draw both the best Lewis structure based on formal charge considerations and the octet abiding Lewis structure. Is either structure consistent with your MO diagram?
Identify all bonding interactions that occur in [BO] - as predicted by (a) MO Theory and (b) hybridization theory. Use the octet abiding Lewis structure for your answer to (b) and use the z- axis as the bonding axis. 2s Energy 2s 2p 2p MOs of [BO] - 𝝈 ?? 𝝈 ?? 𝝅 ?? 𝝅 ?? 𝝈 ?? 𝝈 ?? AOs of B AOs of O Lewis (octet): 𝑯?𝒃/𝑽????: 𝑴? ??????:
Chemical bonding between AOs is orientation dependent and MO structure is influenced by atom identity: HF + + = = In-phase combination Constructive interference e - density between nuclei σ -bond σ *-antibond Node Out-of-phase bonding Destructive interference Greater e - density on ______ Greater e - density on ______ F H F H
3. More EN atom’s AOs are lower in energy greater contribution to bonding MO 4. Less EN atom’s AOs are higher in energy greater contribution to antibonding MO Heteronuclear diatomic molecules: HF Energy 2s 2p 1s AOs of H AOs of F MOs of HF -13.6 eV -18.6 eV -40.2 eV Polarity: Lewis: 1 σ -bond & 3 identical LPs MO Theory: BO = 1 & 3 LPs; only 2 identical LPs 2. Bonding symmetry of orbitals is critical 1. Bonding between 1s H and 2s F is negligible too different in energy! e - density builds up on F due to ________________
We care about relative molecular orbital structure and HOMO/LUMO because these explain reactivity! HF reacts with OH - via acid-base (proton transfer) reaction to make H 2 O and F - Arrows depict e - flow O donates e - pair to H to bond HF bond breaks, shifting e - to F MO says: HOMO of HO - donates e - density to LUMO of HF 𝝈 ? ?,? 𝝈 HF MO Diagram 𝝈 ? ?,? 𝝈 OH - MO Diagram HOMO LUMO Energy HOMO = Highest energy MO containing e - (most reactive e - ) LUMO = Lowest energy unoccupied MO (lowest energy place to put e - )
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