Molecular Bond Theory
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1 Molecular Bond Theory
2 Short comings of the localized electron model: electrons are not really localized so the concept of resonance was added no direct information about bond energies
3 Molecular Orbital Model useful for explaining molecular: electron distribution energy of electrons color magnetic properties paramagnetism diamagnetism
4 Molecular Orbitals (MO s) result from interaction of atomic orbitals (AO s)of the bonding atoms Remember: quantum mechanics focuses on the wave nature of electrons
5 () sigma Bonding two atomic orbitals (AO s) overlap end to end to form two molecular orbitals (MO s) a Bonding Orbital and * Antibonding Orbital
6 Wave interactions constructive interference Bonding destructive interference * Antibonding
7 Molecular-Orbital (MO) Theory In MO theory, we invoke the wave nature of electrons. If waves interact constructively, the resulting orbital is lower in energy: a bonding molecular orbital Pearson Education, Inc. Molecular Geometries and Bonding
8 Molecular-Orbital (MO) Theory If waves interact destructively, the resulting orbital is higher in energy: an antibonding molecular orbital Pearson Education, Inc. Molecular Geometries and Bonding
9 sigma Bonding ( H 2 ) 1s A - 1s B. 1s *. electron density is zero between the nuclei Energy 1s A.. 1s B 1s A + 1s B 1s.. high electron density between the nuclei
10 Bonding Orbitals have lower potential energy than the bonding atomic orbitals * Antibonding Orbitals have higher potential energy than the bonding atomic orbitals low electron density leaves only repulsion between the nuclei
11 Molecular Orbital Electron Configurations We assign electrons to MO,s using the same rules we used to determine atomic electron configurations. aufbau principle Pauli exclusion principle Hund s rule the number of MO s formed is always equal to the number of atomic orbitals combined
12 Bond Order 1 number of electrons in bonding MO s = - 2 ( ) number of electrons in antibonding MO s used to predict the relative stability's of proposed molecules zero or a negative value means the bond has no stability
13 Bond Order H 2 1s 1s * 1s 1s 1/2(2-0) = 1 H 2 + 1s 1s * 1s 1s 1/2(1-0) = 1/2 He 2 1s 1s * 1s 1/2(2-2) = 0 1s He 2 + 1s 1s * 1s 1s 1/2(2-1) = 1/2
14 more stable due to less nuclear and electron repulsion Bond Order H 2 + 1s 1s 1s 1/2(1-0) = 1/2 1s 1s * He + 2 1s 1s 1/2(2-1) = 1/2 1s
15 Homonuclear Diatomic Molecules of the Second Period
16 (π) Pi Bonds two atomic orbitals overlap from side by side positions along the internuclear axis to form Bonding and Antibonding π Orbitals electron density is located above and below the inter nuclear axis
17 Three P orbitals for each element in the second period all of which interact form: p y p y p x p x p z p z two sigma bonds p x and * p x four Pi bonds π p y, π * p y and πp z, π * p z
18 2p z 2p z π * 2p z π2p z 2p x 2p x * 2p x 2p x
19 MO Theory 2012 Pearson Education, Inc. For atoms with both s and p orbitals, there are two types of interactions: The s and the p orbitals that face each other overlap in σ fashion. The other two sets of p orbitals overlap in π fashion. Molecular Geometries and Bonding
20 MO Theory The resulting MO diagram looks like this (Fig. 9.41). There are both σ and π bonding molecular orbitals and σ* and π* antibonding molecular orbitals. Molecular Geometries and Bonding 2012 Pearson Education, Inc.
21 Diamagnetic 2s * Energy Li 2 2s A 2s 2s B
22 Diamagnetic 2s * 2s A 2s B Energy Be 2 2s
23 Expected configuration * 2p x Diamagnetic 2p x 2p y 2p z π * 2p * y π 2p z 2p x 2p y 2p z π2p y π2p z 2p x 2s * 2s A 2s 2s B Energy B 2
24 Actual configuration 2p x 2p y 2p z * 2p x π * 2p y 2p x π * 2p z Paramagnetic 2p x 2p y 2p z π2p y π2p z Energy B 2 2s A 2s * 2s 2s B
25 The 2p x bond concentrates electrons in the same area as the 2s sigma bonds. This increases repulsion's and raises the potential energy of the electrons The π2p y and the π2p z MO s are lower in energy because they exist the outside the internuclear zone
26 2p x 2p y 2p z * 2p x π * 2p y 2p x π * 2p z Diamagnetic 2p x 2p y 2p z π2p y π2p z Energy C 2 2s A 2s * 2s 2s B
27 2p x 2p y 2p z * 2p x π * 2p y 2p x π * 2p z Diamagnetic 2p x 2p y 2p z π2p y π2p z Energy N 2 2s A 2s * 2s 2s B
28 The repulsion's between the 2p x bond and 2s sigma bonds decreases from left to right in the second period. As a result the 2p x bond is lower in energy then the π2p y and the π2p z for the O 2 and F 2 electron configuration
29 2p x 2p y 2p z * 2p x π * 2p y π2p y π * 2p z π2p z Paramagnetic 2p x 2p y 2p z 2p x * 2s 2s A 2s 2s B Energy O 2
30 2p x 2p y 2p z * 2p x π * 2p y π2p y π * 2p z π2p z Diamagnetic 2p x 2p y 2p z 2p x 2s * 2s A 2s 2s B Energy F 2
31 Second-Row MO Diagrams Molecular Geometries and Bonding 2012 Pearson Education, Inc.
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