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lect21_reel5 - Molecular Orbital Theory and Charge Transfer...

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Molecular Orbital Theory and Molecular Orbital Theory and Charge Transfer Excitations Charge Transfer Excitations Chemistry 123 Spring 2008 Dr. Woodward
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H 1s Orbital Molecular Orbital Diagram H 2 Energy H 1s Orbital Bonding Molecular Orbital (Orbitals interfere constructively) Antibonding Molecular Orbital (Orbitals interfere destructively)
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Orbital overlap – Constructive Interference Orbital overlap – Constructive Interference + + -4 -3 -2 -1 0 1 2 3 4 z (Angstroms) Wavefunction ( ) Bonding Overlap 1s Atom 1 1s Atom 2 Atom (2) Atom (1) Constructive Constructive Interference Interference Between the nuclei the wavefunctions add together. Electron density maximized in the internuclear region. This type of overlap leads to formation of a covalent bond. = =
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Orbital overlap – Destructive Interference Orbital overlap – Destructive Interference + + Destructive Destructive Interference Interference Between the nuclei the wavefunctions cancel each other out. Electron density pushed away from internuclear region. This type of overlap works against formation of a covalent bond. -4 -3 -2 -1 0 1 2 3 4 z (Angstroms) Wavefunction ( ) Antibonding Overlap 1s Atom 1 1s Atom 2 Atom (2) Atom (1) = =
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Pi ( Pi ( π π ) Bonding ) Bonding side on overlap side on overlap = = + + Atom 1 p z  orbital Atom 2 p z  orbital Bonding pi  molecular  orbital = = + + Atom 1 p z  orbital Atom 2 p z  orbital Antibonding  pi molecular  orbital Sigma ( σ ) Bonding head on overlap = = + + Atom 1 p y  orbital Atom 2 p y  orbital Bonding sigma 
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