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Chapter Five

This document provides information on molecular orbitals and bonding. It discusses topics like formal charge, oxidation number, types of molecular orbitals including sigma bonds, pi bonds, and delta bonds. It also summarizes molecular orbitals for diatomic molecules like H2, He2, He2+, as well as larger molecules like CO2, H2O, BF3, NH3. The document also briefly discusses molecular shapes, hybridization, and absorption and emission spectra.

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140 views46 pages

Chapter Five

This document provides information on molecular orbitals and bonding. It discusses topics like formal charge, oxidation number, types of molecular orbitals including sigma bonds, pi bonds, and delta bonds. It also summarizes molecular orbitals for diatomic molecules like H2, He2, He2+, as well as larger molecules like CO2, H2O, BF3, NH3. The document also briefly discusses molecular shapes, hybridization, and absorption and emission spectra.

Uploaded by

jayaram234
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Chapter 5

Molecular Orbitals

Formal Charge
f = V L 1/2P where f => formal charge V => number of valence electrons in parent atom L => number of lone pairs of electrons in Lewis structure of molecule P => number of shared electrons

Oxidation Number

Molecular Orbitals
3 types bonding orbitals => B antibonding orbitals => AB nonbonding orbitals => n

Molecular Orbitals
bond order => B.O. B.O. = (B - AB)/2

Molecular Orbitals
magnetism 2 main types diamagnetism => all electrons are paired paramagnetism => one or more unpaired electron, parallel spins on electrons

Sigma Bonds

s-s, s-pz, and pz-pz

Pi Bonds

px-px or py-py

Delta Bond

dx2-y2 - dx2-y2

Molecular Orbitals
For homonuclear diatomics: g (gerade - even) orbital that is identical after inversion sigma bonding, pi antibonding u (ungerade - odd) orbital that changes sign with inversion - sigma antibonding, pi bonding

Molecular Orbitals

sigma bond

pi bond

Molecular Orbitals
HOMO highest occupied molecular
orbital LUMO lowest unoccupied molecular orbital SOMO singly occupied molecular orbital

Diatomic Molecules
AO H MO H2 AO H

1s

1s

ENERGY B - AB 2-0 B.O. = ------------ = -------- = 1 2 2 all electrons are paired, thus diamagnetic

Diatomic Molecules
AO He MO He2 AO He

1s

1s

ENERGY B - AB 2-2 B.O. = ------------ = -------- = 0 2 2

Diatomic Molecules
AO He MO He2+ AO He+

1s

1s

ENERGY B - AB 2-1 B.O. = ------------ = -------- = 1/2 2 2 One unpaired electron, thus, paramagnetic

AO B

MO B2

AO B

2p

2p

2s

2s

1s

nonbonding

1s

AO C

MO C2

AO C

2p

2p

2s

2s

1s

nonbonding

1s

AO O

MO O2

AO O

2p

2p

2s

2s

1s

nonbonding

1s

AO B

MO BN

AO N

2p 2p

2s
2s

1s
nonbonding

1s

AO N

MO NO-

AO O-

2p

2p

2s

2s

1s

nonbonding

1s

Molecular Orbitals for Larger molecules


The orbitals of the surrounding atoms are
collected together to give ligand group orbitals(LGO). Remember the number of ligand group orbitals formed = the number of atomic orbitals used. Find the symmetry labels for these LGOs and the central atom: Determine the point group of the molecule (substitute D2h for Dh and C2v for Cv). Assign x,y,z coordinates to the atoms.

Molecular Orbitals for Larger molecules


For the outer atoms find the characters of the
representation for the combination of the 2s orbitals and for the other sets of orbitals (px, py, pz)(remember if orbital changes position it is given a value of zero, same position 1, same position but different signs -1). (It can also be done on the individual orbitals combination when you draw them)

Molecular Orbitals for Larger molecules


Reduce each representation to irreducible

representations (finding the symmetry of group orbitals). Find the symmetry of the central atom orbitals (it can be easily done by using the character tables for the different orbitals involved). Combine the atomic orbitals of the central atoms with that of the group orbitals with the same symmetry and close energy to form MO (bonding and antibonding). The total # of MOs formed equal the # of AOs used from all atoms.

FHF It has Dh point group. For simplicity D2h will be


used. Look at the expression to the right of the character table for orbitals s, px, py, pz on the fluorine atom and then for their symmetry labels from the left. Draw s, px, py, pz orbitals on the two F atom out of phase and find the symmetry labels by finding the values of the character under the different symmetry operations.

Total # of group orbitals is 8. 2Ag, B2g, B3g, 2B , B B .

FHF H has 1s orbital with symmetry Ag.


Therefore it can combine with the 2 Ag for the group orbitals(s, pz). Both are permitted by symmetry but one is permitted by energy. H(1s)= -13.6, F(1s) -40.2, F(2p) -18.7 eV. The rest of the group orbitals are nonbonding, while H(1s) and F(2pz) give bonding and antibonding MOs. Electrons are distributed according to Afbau rule.

FHF-

FHF-

Carbon Dioxide
The Simpler D2h is used.
The group orbitals for oxygen (surrounding) are the same as for F. 2Ag, B2g, B3g, 2B1u, B2u, B3u. For C the symmetry representation for its orbitals 2s(Ag). 2Pz(B1u), 2py(B2u), 2pz(B3u). Combine orbitals with the same symmetry and
close to give Bonding and antibonding MOs. When there is no match then orbitals are nonbonding. C 2s (-19.4ev) 2p (-10.7eV); O 2s (-32.4 eV) 2p (-15.9eV).

CO2

H2O

BF3

NH3

some bonding and antibonding character

B.O. = 3 CO molecule

CO

SF6

Molecular Shapes
The orbitals of the central atoms are
combined into hybrid orbitals. These hybrids point from the central atom toward surrounding atoms or lone pairs(vectors) Find the reducible representation for these vector hybrids in the symmetry group of the molecule (values of character for each vector is either 1 or 0)

Molecular Shapes
Find the irreducible representation from
the reducible with their symmetry labels Find the orbitals that has the same symmetry labels and with approximate close energies from the expression to the right of the character tables. The hybridization will be the combination of these orbitals.

Molecular Shapes
CH4(sp3hybridiztion) = A1 + T2 NH3(sp3hybridiztion) [PtCl4]2-(dsp2hybridiztion)dx2-y2 orbital is

used) = A1g + B1g+ Eu CO2(sp hybridiztion) SO3(sp2hybridiztion) PF5(dsp3hybridiztion)(dz2 orbital is used)= 2A + E + A2 SO2Cl = 2A + A (3 o orbitals are used)

http://mrsec.wisc.edu/edetc/LED/band.htm

Absorption Spectrum

Emission Spectrum

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