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Molecular Orbital Theory

Linear combination of atomic orbitals


= c11 + c22 + ... If the probability for an orbital is given by 2 and the integral is 1 (2d = 1) then for MO's 2 = c1212 + c2222 + 2c1c212
Or

2 = c12P1 + c22P2 + 2c1c2P12

where P represents the atomic orbital probability

Linear combination of atomic orbitals


integrating gives 2d = c12 + c22 + 2c1c2S12 where S12 is the overlap integral, the sign of which is dependent on the coordinate system. 2 and c 2 give the and character c1 2 1 2

Type of Bonding Interaction


2 = c12P1 + c22P2 + 2c1c2P12
The value of 2c1c2P12 in the region of the bond axis indicates the type of bonding interaction
2c1c2P12 >0 0 <0 interaction bonding non-bonding anti-bonding sign of 2c1c2P12 + -

Type of Bonding Interaction


Types of bonds arise from whether P12 is based on the interaction of one lobe from each AO, two lobes, or four lobes

Molecular Orbital Energies


Successively higher energy orbitals have MO node symmetrically placed, and increasing in number by one, in order from most stable to least stable.

bond type sigma pi delta

# of lobes 1 2 4

AO's used s,s; s,p; p,p; d,d p,p; d,d; p,d d,d

Molecular Orbital Energies


An MO node through an atom means that the AO from that atom does not contribute to the MO.

Molecular Orbital Energies


MO energy increases with increasing numbers of nodes because the net number of bonding interactions decreases by two and the number of nodes increases by one.

Diatomics
H2 and He2has only s orbitals

H2

= c11 + c22

* = c11 - c22

He2

Second Period Diatomics

Bond Order = [# of bonding e- - # of anti-bonding e-]/2

Li

Be

Second Period Diatomics


ps ps

Second Period Diatomics


B2, C 2, N2

OR
sp

sp

Second Period Diatomics


O2 F2

Heteronuclear Diatomics
CO

C O

Orbitals Used
s orbital on the oxygen atom are too low in energy to interact with the s orbital on carbon. Therefore it will be a nonbonding orbital.

Orbitals Used
Due to the rotation axis, only the pz orbital on the O atom has the appropriate symmetry to interact with the s orbital on C.

Orbitals Used
the px and py orbitals on the oxygen and carbon are of the correct orientation to interact.

Orbitals Used
An orbital is left unused on the carbon atom, the pz orbital, which remains as a nonbonding orbital.

Triatomics

Linear Triatomic Molecules


CO2 -- Point group Dh

O C O
x z

C infinity
O C O
x z x z

Orbitals used for Sigma Bonding


s orbitals on the Oxygen atoms are too low in energy to interact with the s orbital on C. Therefore they will be non-bonding orbitals

Orbitals used for Sigma Bonding


Due to the rotation axis, only the pz orbitals on the O atoms have the appropriate symmetry to interact with the s orbital on C.

Orbitals used for Sigma Bonding


the pair of pz orbitals on the oxygens can have two different orientations relative to the C atom.

Orbitals used for Sigma Bonding


The a1g orientation or a1g group orbital can combine with the C s orbital to give a bonding molecular bonding orbital. The a1g set with signs anti bonding reversed can combine with the s orbital to produce an antibonding molecular orbital

a1g

a1g a1u

Orbital Energies

Orbitals used for Sigma Bonding


The C pz orbital also has appropriate symmetry to interact with the pz orbitals on the oxygen atoms. it can interact with the a1u group orbital of the oxygens, to form bonding and antibonding orbitals. a1g will be lower in energy than a1u

Orbitals used in Pi Bonding


The px and py orbitals of the oxygen atoms can be paired two ways

Orbitals used in Pi Bonding

e1u

The px and py orbitals of carbon belong to the two dimensional representation E1u

e1g

Orbitals used in Pi Bonding


The oxygen e1u group orbitals can combine with the carbon e1u group orbital to form bonding and antibonding molecular orbitals

Orbitals used in Pi Bonding


Since the carbon atom does not have any orbitals with a E1g representation, the e1g group orbitals on the oxygen atoms will be non-bonding, and are localized on the oxygen atoms.

bonding e1u anti-bonding

Orbital Energies

Bent Triatomic Molecules


NO2

z x y x z O N y O z x

Orbitals used for Sigma Bonding


Once again the s orbitals on O are different enough in energy from those on N to be non-bonding

Orbitals used for Sigma Bonding


The nitrogen s and pz orbitals have the same representation and so combine with oxygen orbitals as a group orbital (sp hybrid).

Orbitals used for Sigma Bonding


The pz orbitals of the oxygen atoms, similar to a previous case, can have two orientations

Orbitals used for Sigma Bonding


The a1 group orbitals on O can combine with the s and pz orbitals on N, to form three molecular orbitals = (s)N + (pz)N + (pz + pz)O* = (s)N + (pz)N - (pz + pz)O non = (s)N - (pz)N - (pz + pz)O

Orbitals used for Sigma Bonding

Orbitals used for Sigma Bonding


2)The py orbital on N has a b2 representation, and so may combine with the b2 group orbitals of the oxygen = (py)N + (-pz + pz)O* = (py)N - (-pz + pz)O

Orbitals used for Pi Bonding


1)The px orbital on the O atoms can form two group orbitals, b1 and a2. The b1 group orbital can combine with the px orbital of the N atom = (px)N + (px + px)O* = (px)N - (px + px)O

c.Energy level diagram


The a2 group orbitals on O are left as non-bonding, as are the py orbitals.

4Molecular orbital theory using Group Theory--BF3

aSigma bonds
1) Point group D3h 2) Coordinate system for all atoms

3)Effect of symmetry on s bonds Count how many s bands are unchanged using the same symmetry class as that used for s1. is a reducible representation, a combination of A1' and E'

4)Group orbitals by the projection operator method Choose one s orbital and tabulate the results of each operator.

Then multiply these results by the characters of each of the representations found above ca1 = 4s1 + 4s2 + 4s3or s1 + s2 + s3

We can simplify and normalize to get ca1 = (1/3) (s1 + s2 + s3) This set of orbitals looks like:

The other group orbital is e', so multiplying the results above by this representation, gives us e' = 2s2 - 2s3or2s1 - s2 - s3 giving us c(e')a = (1/6) (2s1 - s2 - s3) which looks like

since the E' representation is doubly dimensioned, we expect another e' group orbital by performing a C3 operation and a C32 operation on the first e' group orbital, and subtracting the two, a second e' group orbital is produced. C3

These three group orbitals will combine with three atomic orbitals on Boron which have the same symmetry, to produce three molecular orbitals.

For the first, the a1 group orbital is matched with the s orbital of boron

Pi bonding
The second and third are from combinations of the two e' group orbitals with the px and py atomic orbitals.

We will treat the pz orbitals on the three F atoms the same as s1, s2, and s3. is a reducible representation, a combination of A1" and E"

Choose one ! orbital and tabulate the results of each operator. EC3C3C2C2C2shS3S3svsvsv +!1.+!2+!3-!1.-!3-!2-!1.-!2!3+!1.+!3+!2 Then multiply these results by the characters of

From above (showing only the + lobes) this set of orbitals looks like: This orbital can combine with the pz orbital on B to form the single ! bond.

5Three-centered bonding-Diborane
The e" set of orbitals, will be nonbonding

point group--D2h

Determine the representations of the boron and hydrogen orbitals B = Ag + B2g + B1u + B3u H = Ag + B3u

The Ag and B3u representation will form molecular orbitals, and B2g and B1u will be nonbonding

Use the projection operator method to determine the wave functions.

6Effect of d-orbital participation

7Cyclic planar ! molecules

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