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Molecular Orbital Theory Diatomic molecules: The bonding in F2

Chem 59-250

Each F atom has 2s and 2p valence orbitals, so to obtain MOs for the F2 molecule, we must make linear combinations of each appropriate set of orbitals. In addition to the combinations of ns AOs that weve already seen, there are now combinations of np AOs that must be considered. The allowed combinations can result in the formation of either or type bonds.

The combinations of symmetry:


This produces an MO over the molecule with a node between the F atoms. This is thus an antibonding MO of *u symmetry.

+ 2pzA 2pzB * = 0.5 (2pzA + 2pzB)

2pzA 2pzB * = 0.5 (2pzA - 2pzB)

This produces an MO around both F atoms and has the same phase everywhere and is symmetrical about the F-F axis. This is thus a bonding MO of g symmetry.

Molecular Orbital Theory Diatomic molecules: The bonding in F2

Chem 59-250

The first set of combinations of symmetry:


This produces an MO over the molecule with a node on the bond between the F atoms. This is thus a bonding MO of u symmetry.

+ 2pyA 2pyB

= 0.5 (2pyA + 2pyB)

2pyA 2pyB * = 0.5 (2pyA - 2pyB)

This produces an MO around both F atoms that has two nodes: one on the bond axis and one perpendicular to the bond. This is thus an antibonding MO of *g symmetry.

Molecular Orbital Theory Diatomic molecules: The bonding in F2

Chem 59-250

The second set of combinations with symmetry (orthogonal to the first set):
This produces an MO over the molecule with a node on the bond between the F atoms. This is thus a bonding MO of u symmetry.

+ 2pxA 2pxB

= 0.5 (2pxA + 2pxB)

2pxA

2pxB

* = 0.5 (2pxA - 2pxB)

This produces an MO around both F atoms that has two nodes: one on the bond axis and one perpendicular to the bond. This is thus an antibonding MO of *g symmetry.

Chem 59-250
F

Molecular Orbital Theory MO diagram for F2 You will typically see the diagrams
F2 F
3*u

drawn in this way. The diagram is only showing the MOs derived from the valence electrons because the pair of MOs from the 1s orbitals are much lower in energy and can be ignored. Although the atomic 2p orbitals are drawn like this: they are actually all the same energy and could be drawn like this: at least for two non-interacting F atoms. Notice that there is no mixing of AOs of the same symmetry from a single F atom because there is a sufficient difference in energy between the 2s and 2p orbitals in F. Also notice that the more nodes an orbital of a given symmetry has, the higher the energy.
Note: The the sake of simplicity, electrons are not shown in the atomic orbitals.

1*g 2p
(px,py) pz

Energy

2p 1u

3g

2*u 2s 2g 2s

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F
LUMO

Molecular Orbital Theory MO diagram for F2


F2
3*u

F
Another key feature of such diagrams is that the -type MOs formed by the combinations of the px and py orbitals make degenerate sets (i.e. they are identical in energy).
(px,py) pz

HOMO
2p

1*g

Energy

2p 1u

The highest occupied molecular orbitals (HOMOs) are the 1*g pair these correspond to some of the lone pair orbitals in the molecule and this is where F2 will react as an electron donor.

3g

2*u 2s 2g 2s

The lowest unoccupied molecular orbital (LUMO) is the 3*u orbital this is where F2 will react as an electron acceptor.

Chem 59-250
B

Molecular Orbital Theory MO diagram for B2


B2
3*u

1*g 2p
(px,py) pz

Energy

2p

LUMO

3g

In the MO diagram for B2, there several differences from that of F2. Most importantly, the ordering of the orbitals is changed because of mixing between the 2s and 2pz orbitals. From Quantum mechanics: the closer in energy a given set of orbitals of the same symmetry, the larger the amount of mixing that will happen between them. This mixing changes the energies of the MOs that are produced. The highest occupied molecular orbitals (HOMOs) are the 1u pair. Because the pair of orbitals is degenerate and there are only two electrons to fill, them, each MO is filled by only one electron remember Hunds rule. Sometimes orbitals that are only half-filled are called singly-occupied molecular orbtials (SOMOs). Since there are two unpaired electrons, B2 is a paramagnetic (triplet) molecule.

HOMO

1u

2*u 2s 2g 2s

Chem 59-250

Molecular Orbital Theory Diatomic molecules: MO diagrams for Li2 to F2

Remember that the separation between the ns and np orbitals increases with increasing atomic number. This means that as we go across the 2nd row of the periodic table, the amount of mixing decreases until there is no longer any mixing; this happens at O2). At O2 the ordering of the 3g and the 1u MOs changes. As we go to increasing atomic number, the effective nuclear charge (and electronegativity) of the atoms increases. This is why the energies of the analogous orbitals decrease from Li2 to F2. The trends in bond lengths and energies can be understood from the size of each atom, the bond order and by examining the orbitals that are filled.
Li2 1 2.67 105 d Be2 0 n/a n/a n/a B2 1 1.59 289 p C2 2 1.24 609 d N2 3 1.01 941 d O2 2 1.21 494 p F2 1 1.42 155 d Ne2 0 n/a n/a n/a

In this diagram, the labels are for the valence shell only - they ignore the 1s shell. They should really start at 2g and 2u*.

2s-2pz mixing
Molecule Bond Order Bond Length () Bond Energy (kJ/mol) Diamagnetic (d)/ Paramagnetic (p)

Chem 59-250

Molecular Orbital Theory Ultra-Violet Photoelectron Spectroscopy (UV-PES)

The actual energy levels of the MOs in molecules can be determined experimentally by a technique called photoelectron spectroscopy. Such experiments show that the MO approach to the bonding in molecules provides an excellent description of their electronic structure. In the UV-PES experiment, a molecule is bombarded with high energy ultraviolet photons (usually Ephoton = h = 21.1 eV). When the photon hits an electron in the molecule it transfers all the energy to the electron. Part of the energy (equal to the ionization potential, I, of the MO in which the electron was located) of the photoelectron is used to leave the molecule and the rest is left as kinetic energy (KE). The kinetic energy of the electrons are measured so I can be calculated from the equation:
UV-PES spectrum of N2

I = h - KE = 21.1 eV - KE

eh
UV photon ejected photoelectron

The shape and number of the peaks provides other information about the type of orbital the photoelectron came from. We will not worry about the details, but you can find out more about this in a course on spectroscopy.

N N

N N
ionized molecule

Chem 59-250

Molecular Orbital Theory Diatomic molecules: Heteronuclear molecules

In heteronuclear diatomic molecules, the relative contribution of atomic orbitals to each MO is not equal. Some MOs will have more contribution from AOs on one atom than from AOs on the other. This means that the coefficients in the MO will not be the same! For example, in hydrogen fluoride (HF), some orbitals are derived more from H than F and vice versa. The more the contribution from AOs on a given atom, the higher the coefficient in front of the AO in the MO.

The combinations of symmetry: (note that the 1s orbital on H is closer in energy to the
2pz orbital on F so we will look at that combination because there will be more interaction) This MO is more F-like

+
1sH 2sF

2 = ( 0.1 1sH + 0.9 2pzF)

1sH

+
2pzF
This MO is more H-like

3* = ( 0.9 1sH - 0.1 2pzF)

Chem 59-250

Molecular Orbital Theory

Because the contributions are not equal, the MO diagram will be skewed.

MO diagram for HF

There is a little bit of mixing between the H 1s and the F 2s orbital but it interacts mostly with the 2pz.

F also has the 2px and 2py orbitals that cannot interact with the H 1s orbital because they have the wrong symmetry! If you try to combine these orbitals with the 1s on H, you will find that the overlap integral, S, is equal to 0. Thus these orbitals are exclusively found on the F atom and are called non-bonding. The energies of these orbitals do not change from the energies in the F atom. The orbitals that are derived mostly from F are going to be closer to the energies of the atomic orbitals of F and vice versa.

Chem 59-250

Molecular Orbital Theory

MO diagrams for other heteronuclear diatomics are formed in exactly the same way as that of H-F or those of the homonuclear diatomics: atomic orbitals of appropriate symmetry will to produce MOs. The orbtals that are closest in energy to one another will interact the most - i.e. there will be greater stabilization of the bonding MO and destabilization of the antibonding MO.

In this diagram, the labels are for the valence shell only - it ignores the 1s shell. The labels should really start at 3. Notice, there is no g or u because the molecule does not have a center of symmetry

Again, the MOs will have a larger contribution from one of the atoms. In CO, the HOMO has more of a contribution from C AOs, so CO acts as an electron donor through the carbon atom.

The relative energies of the AOs can be estimated based on the electronegativity of the atoms. More electronegative atoms will have more stable (lower) orbitals.

Molecular Orbital Theory Polyatomic molecules: The bonding in H3+ Each H atom has only a 1s orbital, so to obtain MOs for the H3+ cation, we must make linear combinations of the three 1s orbitals.

Chem 59-250

Consider the situation where the H atoms arranged to make a linear geometry. Note that atoms that are related by symmetry must be treated together.

+
1sA 1sB

+
1sC

0 nodes so most stable. 1g = ( 0.25 1sA + 0.5 1sB + 0.25 1sC) The 1s orbital of HB does not have appropriate symmetry to interact with the combination of 1sA - 1sC. 1 node so less stable than 1g. 1u = ( 0.5 1sA - 0.5 1sC) 2 nodes so this is the least stable of these MOs. 1sC 2g* = (- 0.25 1sA + 0.5 1sB - 0.25 1sC)

+
1sA

no contribution

1sC

1sB

1sA

+
1sB

Molecular Orbital Theory Polyatomic molecules: The bonding in H3+ For the linear cation, the MO diagram would then be:

Chem 59-250

Note that the three H atoms are held together by a total of only two electrons.

Hcentral

H3+

H2(SALC)

H2
Since the terminal H atoms are symmetry related and must be considered as a pair, we must make symmetry adapted linear combinations (SALCs) of their orbitals to interact with the central atom: Opposite phases (u):

2*g

Energy

1u

u g

1s

Same phases (g):

1s
This is the approach that we must use for all polyatomic molecules.

1g

Note that the u combination will be a little bit higher in energy than the g so the nonbonding LUMO is a bit higher in energy than the AO in a free H atom.

BUTsince there are three atoms, a linear arrangement is not the only possibility!

Chem 59-250

Molecular Orbital Theory Polyatomic molecules: The bonding in H3+

Consider the situation where the H atoms arranged in an equilateral triangular geometry. Note that now all the atoms are related by symmetry must be treated together as a set. The symmetry of this arrangement is D3h, which tells us the symmetry of each of the orbitals and also that there must a pair of degenerate MOs.
1sC 0 nodes so this is the most stable MO. a = (1/ 3 1sA + 1/ 3 1sB + 1/ 3 1sC)

+/- +/1sA

+/-

1sB

The doubly-degenerate pair of MOs have e symmetry. Although they do not look alike, each orbital in the pair has the same energy. Notice that the orbitals have roughly the same symmetry as would px and py orbitals in the middle of the H3 ring. Each of these MOs has one node so the e orbital pair will be higher in energy than the a orbital.

e = (1/ 2 1sB - 1/ 2 1sC)

e = (2/ 6 1sA - 1/ 6 1sB - 1/ 6 1sC)

Molecular Orbital Theory Polyatomic molecules: The bonding in H3+ For the triangular cation, the MO diagram would then be:

Chem 59-250

3H

H3+

Notice that the e pair must have identical energies and that the pair is less stable than either the free atoms or the a MO so it can be called anti-bonding.
1e*

Energy

Again, the three H atoms are held together by a total of only two electrons. Furthermore, there is no central atom and each H is related by symmetry. Because of this, the use of SALCs and MO theory can provide us with a much better model of the bonding than we could get from VBT and the localized model of bonding.

3 1s 1a

BUTin theory, we could have any arrangement in between the linear and the triangular, so how do we find out which geometry is the most stable?

HA

HB

HC

HA

HB

HC

HB HA HC
A

HB H HC

Chem 59-250

Molecular Orbital Theory Polyatomic molecules: The bonding in H3+

We can use a Walsh diagram to compare assess the relative energies of different possible structures. In a Walsh diagram, the relative energies of important MOs are plotted as the value of a metrical parameter (e.g. bond lengths or angles) is changed. The amount of stabilization or destabilization of the MOs is based on the amount of increase or decrease in the in-phase overlap of the AOs used to make each molecular orbital. Walsh diagram for Dh to D3h

In the example of H3+ there are only two electrons, thus we only have to examine how the energy of the lowest orbital (1 to a) varies with the change in angle. From the diagram we can see that the energy decreases from Dh to D3h so the electronic energy of the triangular arrangement will be lower than that of the linear arrangement. This means that the triangular form will be the most stable arrangement. If there were more electrons, we would have to consider how the energies change for any orbital that might be populated with electrons.

Chem 59-250

Molecular Orbital Theory Polyatomic molecules


e.g. BeH2

The steps you can use to build a MO diagram for any polyatomic molecule are: 1. Determine the symmetry of the molecule and figure out which atoms are symmetry related. 2. Make appropriate symmetry adapted linear combinations of atomic orbitals for the symmetry related atoms. 3. Estimate the energies of the AOs using the electronegativities of the atoms. 4. Use symmetry to determine which orbitals can interact with each other to form bonding and antibonding MOs. Those that cant interact will be nonbonding. 5. Arrange MOs in order of increasing energy based on the number of nodes and use the available electrons to fill the lowest energy orbitals. For simple molecules, you can draw pictures of the SALCs and MOs (as shown) in the example. For more complicated molecules, it is easier to just use symmetry and character tables.

Chem 59-250

Molecular Orbital Theory Polyatomic molecules

If you are trying to estimate the appropriate geometry for a triatomic molecule using a Walsh diagram, all that is necessary is to correctly determine the number of electrons that will populate the orbitals in the diagram. Then you can estimate which electron configuration will provide the lowest overall energy (and thus the most stable geometry). E.g.s: There are 4 valence electrons in BeH2 so these electrons can fill the 1g and the 1u orbitals in the diagram (shown in blue). The lowest energy combination is obtained when the bond angle is 180. In H2O, there are 8 valence electrons which will fill up all four orbitals in the diagram. Since the energy of the 1b1 orbital doesnt change as the angle is changed, the overall energy is mostly determined by the relative energies of the 2a1 and the 1b2. A reasonable guess is shown in red. Orbital overlap analyses such as these allow for the prediction of molecular geometry using the delocalized model for covalent bonding in the same way that VSEPR is used in the localized approach.

Chem 59-250
1. The point group is C3v.

Molecular Orbital Theory Polyatomic molecules

E.g. Buiding a MO diagram for NH3:

2. All Hs are related so these must be split into SALCs of a and e symmetry (these have exactly the same shape as those in the example for H3+, but the point group that must be used for NH3 is C3v). 3. XN 3 and XH 2.2 so the energy levels of the AOs on N will be lower than those on the H atoms. 4. From the C3v character table, the symmetry of the AOs on N are: A1(2s), A1(2pz), and E(2px,2py). Each of these orbitals can interact with the SALCs from the H atoms. 5. Fill the MOs with the 8 valence electrons. In NH3, the HOMO is a mostly nitrogen-based orbital that corresponds to the lone pair of electrons from VBT. This is why ammonia acts as a Lewis base at the N atom. The LUMO is the 2e level that has more H character - this shows why NH3 can also act as a Lewis acid through the H atoms.

HOMO

LUMO

Chem 59-250

Molecular Orbital Theory Polyatomic molecules


Si SiH4
2a1* 2t2*

E.g. Buiding a MO diagram for SiH4: 1. The point group is Td. 2. All Hs are related so these must be split into SALCs of a1 and t2 symmetry (these are harder to draw, so its easier to use a symmetry analysis of the four H atoms to get the SALCs for AOs of the H atoms). 3. XSi 1.9 and XH 2.2 so the energy levels of the AOs on the H atoms will be lower than those on the Si atom. 4. From the Td character table, the symmetry of the AOs on Si are: A1(3s), T2(3px,3py,3pz). Each of these orbitals can interact with the SALCs from the H atoms. 5. Fill the MOs with the 8 valence electrons. In SiH4, the HOMO is a mostly based on the peripheral hyrogen atoms and the LUMO is dominated by Si so SiH4 will act as an electron donor through the H atoms and an electron acceptor at Si.

4H

3p T2 1t2 3s A1 1a1

Chem 59-250

Molecular Orbital Theory Polyatomic molecules

Consider what happens to the -bonding MOs if the symmetry is reduced from Td to C2v: there will no longer be triply-degenerate MOs. The four bonding orbitals are split into two sets - those with more H character (higher in energy) and those with more Cl character (lower in energy).

CH4
2a1*

4H

CH2Cl2
4a1* 2b2*

2 H, 2 Cl

2t2* 2b1* 2p T2 1t2 2s 2s A1 1a1 1b2 2a1 A1,B1 1b1 1a1 A1,B2 2p 3a1*

2H

2 Cl

Since these diagrams are only concerned with the -bonding, the AOs and MOs from the 3p orbitals on Cl have been omitted. The correlation lines from the 2p orbitals are not drawn for clarity.

Chem 59-250

Molecular Orbital Theory Pi-bonding in polyatomic molecules

Molecular orbital theory considers -bonding in exactly the same way as -bonding. Orbitals with appropriate symmetry will interact to form bonding and anti-bonding MOs. In contrast to Lewis theory or VBT, resonance structures are not needed to describe the -bonding because the MOs are spread equally over the -system of the entire molecule. Not surprisingly, the delocalized model of bonding provides a much better picture of the delocalized -system. E.g. the -bonding in CO3-2 In the D3h molecule, the 2pz orbitals on the O atoms give SALCs of the following form: The 2pz orbital on C can only interact with the a2 SALC to give bonding and anti-bonding MOs.

These are analogous to the SALCs we built for H3+ and so the normalization coefficients are identical:
a2 = (1/ 3 2pzA + 1/ 3 2pzB + 1/ 3 2pzC) e = (1/ 2 2pzB - 1/ 2 2pzC) e = (2/ 6 2pzA - 1/ 6 2pzB - 1/ 6 2pzC)

A MO diagram of the -bonding:

Chem 59-250

Molecular Orbital Theory Pi-bonding in aromatic molecules

The -bonding in aromatic molecules is readily predicted using MO theory. Although the details of the treatment that predicts the energies is better left to a higher level course, the symmetry and relative energies of the MOs are easily understood from the number of nodes in each of the MOs. The -bonding in C5H5-1 (aromatic) The -bonding in C3H3+1 (aromatic)
2 nodes 1 node 1 node 0 nodes 0 nodes

The -bonding in C4H4+2 (aromatic)


2 nodes 1 node

The -bonding in C6H6 (aromatic)


3 nodes 2 nodes

0 nodes 1 node

Aromatic compounds must have a completely filled set of bonding -MOs. This is the origin of the Hckel (4N+2) -electron definition of aromaticity.

0 nodes

Chem 59-250

Molecular Orbital Theory Infinite polyatomic molecules

An adaptation of MO theory is also used to treat extended (essentially infinite) molecular systems such as pieces of a metal (or an alloy) or a molecule such as a diamond. Remember that whenever atomic orbitals have appropriate symmetry and energy, they will interact to form bonding and anti-bonding MOs. We have only considered small molecules but there are essentially no limits to the number of atoms that can mix their corresponding AOs together. This mixing must occur because of the Pauli exclusion principle (i.e. so that no two electrons in the solid have the same quantum numbers).
MO anti-bonding As the number of interacting atoms (N) increases, the new bonding or anti-bonding MOs get closer in energy.

AO(1)

AO(2) bonding

In the extreme, the MOs of a given type become so close in energy that they approximate a continuum of energy levels. Such sets of MOs are known as bands. In any given band, the most stable MOs have the most amount of bonding character and the highest energy MOs are the most anti-bonding. The energy difference between adjacent bands is called the band gap.

Chem 59-250

Molecular Orbital Theory

Remember that the closer to AOs of appropriate symmetry are in energy, the more they interact with one another and the more stable the bonding MO that will be formed. This means that as the difference in electronegativity between two atoms increases, the stabilization provided by covalent bonding decreases (and the polarity of the bond increases). If the difference in energy of the orbitals is sufficiently large, then covalent bonding will not stabilize the interaction of the atoms. In that situation, the less electronegative atom will lose an electron to the more electronegative atom and two ions will be formed.
AO(1)

AO(1)

AO(1) AO(1) AO(2) AO(2) AO(2) AO(2)

Most covalent
X < 0.5 : covalent

Polar Covalent
2 > X > 0.5 : polar

Ionic
X > 2 : ionic

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