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# of lobes 1 2 4
AO's used s,s; s,p; p,p; d,d p,p; d,d; p,d d,d
Diatomics
H2 and He2has only s orbitals
H2
= c11 + c22
* = c11 - c22
He2
Li
Be
OR
sp
sp
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
O C O
x z
C infinity
O C O
x z x z
a1g
a1g a1u
Orbital Energies
e1u
The px and py orbitals of carbon belong to the two dimensional representation E1u
e1g
Orbital Energies
z x y x z O N y O z x
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