2-43

Heteronuclear Molecules
The relative energy of the bonding orbitals determines the magnitude of the covalent bond energy (Ecov):

2-44

Energy Level Diagram of CO

2-45

Hydrogen Fluoride
In H-F the 1s orbital of H is energetically well above the 1s and 2s orbitals of F > it interacts only with the 2pz orbital (all remaining electrons are in non-bonding orbitals!)

2-46

Lithium Fluoride
As the polarity difference between two atoms increases, the orbital energy difference also increases > electrons shift towards the more electronegative atom Limiting case: Ionic compounds
Ionic crystal: Ions are held together in a 3-dimensional lattice by combination of electrostatic and covalent interactions

2-47

Homonuclear Bond Energies

Note: Values can vary considerably depending on compounds involved

Bond becomes weaker with increasing atom size But: First row elements of group 15, 16 and 17 form weaker bonds than 2nd row elements (repulsion between lone pairs more pronounced) Group 1&2: Destabilizing + charges when mutually bonded Energy of CC to NN sharply decreased due to presence of lone pairs

2-48

Heteronuclear Bond Energies

Heteronuclear bond energies much higher (stronger bonds) than homonuclear energies (due to electronegativity differences) Group 2 bonds stronger than group 1 (ionic bond: lattice energies proportional to ion charges) BF stronger than AlF due to interaction SiF stronger than CF: large difference in electronegativity, interaction with vacant d orbitals of Si

2-49

Multiple Bond Energies

N2 triple is very strong (only the CO triple bond is stronger) N=N is more than twice the bond energy of a NN single bond But: P=P is less than twice the bond energy of the PP bond > bond interaction for 2nd and 3rd row elements weaker (due to larger and more diffuse p orbitals) > PP single bond considerably stronger than NN (or OO) (less repulsion of lone pair electrons)

2-50

Molecular Orbitals of Polyatomic Molecules

Concept of linear combination can be also applied to polyatomic molecules > the resulting MOs are delocalized over the entire molecule Symmetry analysis by group theory predicts those linear combinations, which lead to bonding, anti-bonding or nonbonding MOs The energy of the resulting MOs is measured via photoelectron spectroscopy or estimated with quantum chemical calculations

2-51

Beryllium Dihydride (BeH2)

VSEPR analysis: linear geometry Set of AOs: Be: H: Note: the 2px and 2py orbitals yield non-bonding interactions Form group orbitals with 1s orbitals of H and H:

B = 1s ( H ) 1s ( H' )

A = 1s ( H ) + 1s ( H' )

2-52

Group Orbitals Interact with Be AOs:

A interacts with the 2s orbital of Be to form a bonding (s) and anti-bonding (s*) orbital:

B interacts with the 2pz orbital of Be to form a bonding (p) and anti-bonding (p*) orbital:

2-53

Energy Level Diagram

energy Group orbitals

B A

2-54

MOs of Water (H2O)

VSEPR analysis: bent geometry Set of AOs: O: H: Note: the 2py orbital results a non-bonding interactions Form goup orbitals with 1s orbitals of H and H:

B = 1s ( H ) 1s ( H' )

A = 1s ( H ) + 1s ( H' )

2-55

The Two A Group Orbital Interactions:

A interacts with two AOs of Oxygen: The 2s and 2pz orbital:

> this results in one bonding, one anti-bonding and one non-bonding (approximately) orbital:
Oxygen AOs

s,z* s,z nb A
(Group Orbital)

2pz 2s

s,z

2-56

The B Group Orbital Interaction:

B interacts with the 2px orbital of oxygen to form a bonding (s) and anti-bonding (s*) orbital:

2px

2-57

To Give the Final Energy Level Diagram...

Group orbitals energy

B A

2-58

Diagram with MO shapes

2-59

Hybridization
Molecular Orbital Theory: > Electrons are delocalized over entire molecule (including core shell electrons!) Hybrid Orbital Description: > Valence bond approach > Bonds described as localized interactions of TWO electrons Bonding between two atoms can be also described as overlap of two hybrid orbitals, which represent the correct valence geometries
A hybrid orbital is a linear combination of AOs of a SINGLE atom Different linear combinations will result different geometries

2-60

Hybrid Orbitals

2-61

Linear Geometry
Beryllium Hydride
Linear combination of one 2s and one 2p orbitals results two sp hybrid orbitals:

sp(1) =

1 (2 s + 2 pz ) 2

sp(2) =

1 (2 s 2 pz ) 2

promotion

2-62

Linear Geometry
Ethyne (HCCH)

The two remaining p orbitals contain one electron each > Delocalization of these two electrons results two orbitals with symmetry (with 90 angle between each other):

2-63

Trigonal Geometry
Boron Trihydride:

The remaining 2pz orbital is perpendicular to the the three hybrid orbitals and is not occupied

2-64

Trigonal Geometry
Ethene (H2CCH2):

The remaining two 2px orbitals is perpendicular to the the three hybrid orbitals and contain one electron each > Delocalization results one additional orbital with symmetry

2-65

Tetrahedral Geometry
Methane (CH4)

The 2s and three 2p orbitals of carbon result four sp3 hybrid orbitals

2-66

How useful are hybrid orbitals?

Provides a qualitative picture of the bonding around an atom Purely mathematical concept Hybridization arguments are not predictive, just descriptive! MO theory is predictive, but complicated to use

2-67

Frontier Orbitals
Many properties of molecules can be interpreted through the use of the molecular orbital model, and in particular by looking at the frontier orbitals: the HOMO (highest occupied molecular orbital) > Donor orbital the LUMO (lowest unoccupied molecular orbital) > Acceptor orbital The energy difference between the HOMO and LUMO corresponds to the lowest excitation energy

2-68

Conjugated Systems
When two or more double (or triple) bonds are close to one another, the valence electrons tend to mingle together > the MO model with its emphasis on delocalization explains this effect better than the localized valence bond approach:

Ethene:

*
H H H H

2-69

Conjugated Sytems
Butadiene:
*
3 nodes

*
H H H H H H

2 nodes

1 node

Carbon: sp2 hybridized

no node

2-70

Energy Levels
With increasing number of orbitals, the energy levels get closer and closer > the energy difference between HOMO and LUMO is decreasing > excitation by a small electric potential or by light will move electrons into the LUMO orbitals, ready to convey a current (if a potential difference is imposed) > semiconducting properties

2-71

Cyclic Structures

2-72

August Kekul had a dream...

Benzene was isolated 1823 from distillation of whale oil by Michael Faraday (named bicarburet of hydrogen) The structure was an unsolved puzzle until 1865, when Kekul dreamed of carbon-chain snakes and finally proposed the correct structure Some older versions of benzene:

2-73

Resonance Structures of Benzene

There are two possible resonance structure for benzene:

> each carbon has sp2 hybridization, the remaining 6 p-orbitals combine to give 6 delocalized MO orbitals

2-74

MO Energy Diagram

3 nodes

*
Energy

2 nodes

1 node

no node

2-75

Large Conjugated Sytems

Graphite consists of layers of fused 6-membered carbon rings (sp 2 hybridized) with an interlayer spacing of 335 pm (sum of carbon radii) The remaining unhybridized p-orbitals participate in extensive bonding, with electron density delocalized over the layers Bond distance: 142 pm = bond order of 1.333

At very high pressure graphite can be converted to diamonds, another allotrope of carbon All carbon atoms are sp3 hybridized, there are no delocalized electrons > diamond is an insulator

2-76

Buckminster Fullerene
In 1985 another allotrope of carbon (C60) was discovered via pulsed laser vaporization of graphite It was named after the architect Buckminster Fuller All 60 carbons are sp2 hybridized, leaving 60 p-orbitals to give 60 MOs (spread over both sides of the surface)

2-77

Natural Products
Many colored compounds in nature consist of large, delocalized -systems The HOMO-LUMO energy difference in these molecules is small enough to absorb light in the visible region

N Mg H3 C H N

N
beta-carotene (orange)

H3CO O O O

Note: The color of a material is complementary to the absorbed light > beta carotene is orange, and therefore it absorbs strongly in the blue and violet region of the spectrum

Chlorophyll (green)

2-78

Photosynthesis
The green color of plants is due to absorption of light by chlorophyll pigments > the absorbed energy is used to convert CO2 to carbohydrates (sugars), oxygen is produced as a side product