Chapter IV , Part 4 Electronic structure of the molecule
IV.2.3. Molecular orbital diagrams
Molecular orbital diagrams are graphical representations used in quantum chemistry to visualize and understand the interactions
between atomic orbitals and the formation of molecular orbitals in a molecule. The filling of molecular orbitals in the diagram is
done according to the following three rules:
• Klechkowski's rule states that the lowest-energy orbitals must be filled before moving to higher-energy orbitals when filling
electrons in a molecule.
• Pauli's exclusion principle states that each molecular orbital can hold a maximum of two electrons, and these electrons must
have opposite spins.
• Hund's rule states that when there are multiple degenerate molecular orbitals available, electrons must be distributed so that
each orbital contains one electron with the same spin before pairing them with opposite spins.
The bond index, bond number, or bond order is defined by:
number of electrons in bonding MOs - number of electrons in antibonding MOs
Bond index =
2
Bond order corresponds to the number of bonds between atoms. A bond order of 1 indicates a single bond, where a pair of
electrons is shared between the two bonded atoms. A double bond has a bond order of 2, meaning that two pairs of electrons are
shared. Similarly, a triple bond has a bond order of 3, indicating three pairs of shared electrons. For a bond to be stable, the bond
order must be strictly positive. If the bond order is negative or zero, the chemical bond is unstable and tends to break.
IV.2.3.1. Diagrams of homonuclear molecular orbitals:
These diagrams are used to represent the molecular orbitals formed by the combination of atomic orbitals of two identical atoms
(A2) or atoms with similar electronegativities. Example of the molecule O2 In the case of oxygen, the interaction between s and p
orbitals is considered weak. Only the atomic orbitals of the valence shell of the atoms will be involved in the formation of bonds
and, therefore, the formation of molecular orbitals. The electronic configuration of the oxygen atom 8O is: 1s22s22p4, the atom has
6 valence electrons. The energy diagram of molecular orbitals is given in the figure below. According to figure 6, the molecule
(O2) is paramagnetic because it has 2 unpaired electrons in its molecular orbitals π*x and π*y. The electronic configuration of the
molecule, considering only the valence shell, is written as follows:
σs2, σs*2, σz2 , (π2x ,π2y) , (π*1x ,π*1y).
Bond index = (8 − 4) / 2 = 2 bonds
Figure 6 : MO diagram for O2
Example of the N2 molecule
In this case, the interaction between the s and p orbitals is considered significant, leading to a slight modification of the energy
diagram of molecular orbitals. The electron configuration of the atomic nitrogen 7N is: 1s22s22p3, and the atom has 5 valence
electrons. The energy diagram of the N2 molecule is represented below. The N2 molecule is diamagnetic, meaning it does not have
any unpaired electrons and is repelled by an external magnetic field.
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Chapter IV , Part 4 Electronic structure of the molecule
Figure 7 : MO diagram for N2
The electron configuration of the molecule, considering only the valence shell, is written as follows:
σs2, σs*2, (π2x ,π2y), σz2
Bond index = (8 − 2) / 2 = 3 bonds
Example of the compound He2
The atomic orbitals (A.O.) to consider are the 1s orbitals of He, occupied by two electrons, since the electron configuration of He
is 1s2. The atom has 2 valence electrons. The energy diagram of the He2 compound is shown below (Figure 8).
According to Figure 8, the bond order = 1/2 (2 - 2) = 0
He2 is less stable than He, so it does not exist.
Figure 8 : MO diagram for He2
IV.2.3.2. Diagrams of heteronuclear molecular orbitals
These diagrams are graphical representations that show the combination of atomic orbitals from different atoms in a heteronuclear
molecule (meaning a molecule composed of atoms with different electronegativities).
The difference between the MOs of homonuclear and heteronuclear molecules lies in the electron density (electron cloud), which
is dense on the side of the more electronegative atom in the bonding MOs.
For example the NO compound
In the case of NO, the interaction between s and p orbitals is significant. The more electronegative atom (O) is more charged than
that of (N), and the energy levels of the AOs of (O) are lower than those of (N). The energy diagram of NO is illustrated below
(Figure 9).
Electronic configuration of NO : σs2 σs*2 (π x2 π y2) σz2 πx*1
Bond index : (8 - 3) / 2 = 2,5 bonds,
According to the electron configuration of NO, the molecule is paramagnetic as it possesses a lone electron in the πx* orbital.
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Chapter IV , Part 4 Electronic structure of the molecule
Figure 9 : Molecular orbital (MO) diagram for NO
Notes :
The Bond Order or index (BO or BI) provides information about the strength of the bond between bonded atoms. A higher bond
order corresponds to a stronger bond and a closer bond between atoms. Double and triple bonds are generally stronger than single
bonds due to increased electron sharing. Consequently, the bond length decreases with an increase in bond order.
In the following diagram (Fig 10) , the energy diagrams of the Molecular Orbitals (MO) are provided for the species: O2 , O +2 , et
O −2.
According to figure 10, the bond index BI (O2) = (8 - 4) / 2 = 2 bonds
BI (O +2) = (8 - 3) / 2 = 2,5 bonds
BI (O −2) = (8 - 5) / 2 = 1,5 bonds
BO (O +2) > BO (O2) > BO (O −2) this means that d (O +2) < d(O2) < d (O −2)
The dissociation energy follows the same order as the bond index. This means that the higher the bond index, the higher the
dissociation energy of the bond. In other words, bonds with a higher bond index are more energetically stable and require mor e
energy to be broken.
Figure 10 : MO diagrams for O2 , O +2 , and O −2
IV.2.4. Polyatomic molecules - Hybridization Theory
Hybridizations: sp, sp2, and sp3
We will illustrate this by studying simple compounds of carbon and hydrogen.
Hybridizations sp3: This hybridization model proves particularly useful for describing single covalent bonds.
Taking the example of methane : CH4
Carbon (6C) in the ground state has the following electronic configuration : 1s22s22p2
It possesses two unpaired electrons in the p subshell.
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Chapter IV , Part 4 Electronic structure of the molecule
This valence state does not allow carbon to form the four bonds with hydrogen atoms. For this reason, it must transition to the next
excited state:
Excited Carbon C*: 1s22s12p3
2s 2px 2py 2pz
Lewis Diagram of CH4:
These four bonding pairs (bonds) are identical, which aligns well with the formation of four new hybrid orbitals: the 2s orbital
mixes with the three 2p orbitals to form four sp3 hybrid orbitals. The excited carbon atom becomes:
C* : 1s22s12p3
sp3 sp3 sp3 sp3
In sp3 hybridization, the three p atomic orbitals of the carbon atom are combined with its s atomic orbital, resulting in four similar
hybrid orbitals pointing towards the four directions of a regular tetrahedron (the directions are 109.28◦ apart from each other).
The molecule CH4 is formed by the axial overlap of the four sp3 hybrid orbitals of carbon (C) with the four 1s orbitals of hydrogen
(H), thus creating four sp3 - s type overlaps, forming the four σ bonds.
• The molecular geometry is determined by the shape and orientation of the hybrid orbitals, which differ from the shape and
orientation of atomic orbitals.
sp3 hybridization should apply not only to AX4-type structures (such as CH4) but also to
structures of the type AX3E (such as NH3) or AX2E2 (such as H2O).
NH3
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Chapter IV , Part 4 Electronic structure of the molecule
H2O
In methane, the molecule's geometry is a regular tetrahedron, with a bond angle of 109.28°. The C−H bond length in methane is
1.10 Å.
sp2 Hybridization: The sp2 hybridization model is particularly useful for describing double covalent bonds.
Taking the example of the C2H4 molecule: The carbon (6C) in its ground state has the following electron configuration: 1s22s22p2,
with two unpaired electrons in the p subshell.
This valence state does not allow each carbon to form bonds with both hydrogen atoms and the second carbon. For this reason, it
must transition to the following excited state:
Excited carbon: C* : 1s22s12p3
2s 2px 2py 2pz
In ethylene, each carbon atom must be sp2 hybridized as it is surrounded by three bonded atoms. sp2 hybridization involves
combining the two p atomic orbitals of each carbon atom (C) with its s atomic orbital.
The excited carbon atom becomes
C* : 1s22s12p3
sp2 sp2 sp2 2p (orbitale pure)
In ethylene, C-H bonds are formed by the axial overlap between the sp2 orbitals of carbon atoms and the s orbitals of hydrogen
atoms, thus creating a σ bond.
The carbon atoms are connected by two non-equivalent bonds:
The first C-C bond is formed by axial overlap between the sp2 orbital of one carbon and the sp2 orbital of the other
carbon, creating a σ bond.
The second C-C bond results from the lateral overlap of the non-hybridized p orbitals of each carbon atom, creating a π
bond. This π bond is perpendicular to the plane formed by the sp2 orbitals and is generally weaker than the σ bond.
In the ethylene molecule, the C−H bond length is 1.08 Å, and the C=C bond length is 1.33 Å. The geometry defined for each
carbon is triangular, with an HCC angle of 121.7°. The molecule is planar due to the presence of the C=C double bond, which
prevents free rotation around the carbon axis.
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Chapter IV , Part 4 Electronic structure of the molecule
Hybridation sp: This hybridization model is particularly useful for describing triple covalent bonds. Taking the example of the
acetylene molecule: C2H2 Carbon in its ground state transitions to the excited state: C*: 1s22s12p3
Since each carbon is surrounded by two atoms (H and C), it must undergo sp hybridization.
C* : 1s22s12p3
sp sp p p
In acetylene, C−H bonds are formed by the axial overlap of sp orbitals from carbon atoms with the s orbitals of hydrogen atoms,
thus creating σ bonds. Carbon atoms in acetylene are connected by three bonds:
A C−C bond is formed by the overlap of sp orbitals from one carbon with the sp orbital of the other carbon, creating
another σ bond.
The other two bonds result from the lateral overlap of the non-hybridized p orbitals of each carbon, creating two π bonds.
In the acetylene molecule, the length of the C−H bond is 1.06 Å, and the length of the C≡C bond is 1.20 Å. The molecule is linear
due to the presence of the triple bond C≡C, resulting in an HCC angle of 180°.
The type of hybridization can be determined from the Lewis model by counting the number of σ bonds and the number of non-
bonding pairs around the central atom. By summing these two values, one can deduce the hybridization of the central atom.
If the sum is 4, it corresponds to sp3 hybridization. Examples:
If the sum is 3, it corresponds to sp2 hybridization. In the molecule CH4, the sum is 4: carbon is sp3 hybridized.
If the sum is 2, it corresponds to sp hybridization. In the molecule NH3, the sum is 4: nitrogen is sp3 hybridized.
In the molecule H2O, the sum is 4: oxygen is sp3 hybridized.
In the molecule C2H4, the sum is 3: carbon is sp2 hybridized.
In the molecule C2H2, the sum is 2: carbon is sp hybridized.
Acetonitrile, or methyl cyanide, is a chemical compound with the formula CH3CN. This colorless liquid is often used as a solvent.
Its chemical structure is represented below.
Acetonitrile
In this molecule, counting the number of σ bonds and non-bonding pairs around each central atom gives the following
hybridizations:
Carbon C1 has a sum of 2, indicating sp hybridization.
Carbon C2 has a sum of 4, indicating sp3 hybridization.
Nitrogen has a sum of 2, indicating sp hybridization.
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