Molecular Orbital Therory-Diatomic Molecules

Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus
Molecular Orbital Theory of Covalent Bond
1. Introduction
All bonding theories are based on fact that molecules are made of atoms. Molecule is a
chemical species made up of combination of two or more atoms of same element or different
elements. Example-
H + H → H2
H2 + ½ O2 → H2O
We know that electron in atoms have definite arrangement and they are accommodated
in orbitals. According to VBT: a) Orbitals of the atoms overlap with each other to form a bond.
b) In a molecule, orbital of an atom retains their individual characteristics. c) With the help of
concept of hybridization of atomic orbitals one can explain the shape of molecules. Valence
bond model is simple model to explain bonding and an excellent model to explaining
molecular structure. As such, VBT is useful over the Lewis structure and VSEPR model.
VSEPR model helps us to visualize structure of molecule. VBT added better understanding of
the nature of the chemical bonding in molecules. VBT added the simplicity of Lewis structures
and the relatively straightforward concept of hybridization to explain structure of the
molecules.
Valence bond model is able to explain the bonding in diatomic and some polyatomic
molecules but do not able to explain some of the quantitative properties of molecules such as
magnetism and spectral properties of molecules. Even it is unable to explain bond lengths in
some of the polyatomic molecules. To some extent by adding the resonance concept it is
explained but it is only qualitative explanation. Therefore, alternative model, known as
Molecular Orbital Theory (MOT), was introduced by the American physicist Robert
Mulliken (and others) around 1932. MOT is based on the Quantum Theory
Postulates of MOT are -
i. It considers that atoms in molecules are held together at their equilibrium position by
delocalized electrons. i.e. electrons of bonded atoms delocalized over the molecule
(electrons can move all over the molecule). Valence electrons of atoms take part in bonding
and they are considered to associated with all atoms in the molecule.
ii. In the molecule, atomic orbitals combine to form Molecular Orbitals (MO’s). MO’s have
different shape than atomic orbitals.
iii. Molecular orbitals are delocalized (spread) over all the atoms of molecule hence atoms are
held together.
iv. The combination of atomic orbitals to form molecular orbitals is not arbitrary but only
definite orbitals from atoms can combine to form molecular orbitals. AO’s of same
symmetry and energy combine to form MO’s.
vi. The method was developed for combination of atomic orbitals (AO’s) to form MO’s and it
is based on the Schrödinger equation. Electron has particle as well as wave nature. By
considering wave nature of electron, the combination of atomic orbitals is possible to form
MO’s.
vii. Electrons in the AO’s used to form MO’s are filled into MO’s in the molecule. Electrons
are filled into MO’s according to Aufbau principle and Hund’s rule of maximum
multiplicity.
2. LCAO method
The combination of AO’s of different atoms to form MO’s can be explained on the
basis of quantum theory. One of the methods of quantum theory to explain formation of MO’s
1 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

is Linear Combination of Atomic Orbitals (LCAO). It is an approximate solution Schrödinger

equation hence also called as LCAO approximation.
Consider two atoms hydrogen atoms HA and HB forming H2molecule. The 1s orbital of
each atom combine to form MO’s. The electron in 1s orbital can be described by wave function
Ψ. The wavefunction for the electron in atom HA - ΨA and for atom HB - ΨB. When the two
atoms approach towards each other, then at bonding distance, the electron clouds of these two
atoms fuse together to form MO’s. Then, wave function for the molecule(Ψ) can be obtained
by a linear combination of the atomic orbitals.
Ψ = C1Ψ A + C2ΨA ----------------- (1)
Where, i) Ψ is the wavefunction of molecular orbital
ii) Ψ A and ΨB is the wavefunction for a 1s AO.
iii) C1 and C2are the constants. These are the adjustable parameters of our trial
wavefunction of MO. Because the energies of the two 1s AOs for each H atom
are identical, C1=C2.C1 and C2are chosen to have minimum energy of MO’s.
The probability of finding the electron in MO is definite and its maximum value will be
1. Thus, we can modify the equation 1 as follows:
Ψ = N(C1ΨA + C2ΨB) ----------------- (2)
Where, N is called as normalization constant.
The normalization constant is so selected that the probability of finding the electron in
MO is unity (i.e. 1). Now we have to find out the probability of finding the electron in small
volume dv in molecule. It can be obtained by taking the square of wave function of MO. (It is
same as that of atom. We derive AO by taking square of wave function of electron (Ψ) by
considering probability 1). Therefore, equation 2 become as follows:
Ψ2 = [N(C1ΨA + C2ΨB)]2
= N2(C1ΨA + C2ΨB)2
= N2(C12ΨA2 + 2C1C2ΨAΨB + C22ΨB2) ----------- (3)
The importance of the terms in equation – 3:
i. C12ΨA2represents the probability of finding the electron in atom HA
ii.C22ΨA2represents the probability of finding the electron in atom HB
iii.2C1C2 ΨAΨB represent the overlap between the two atomic orbitals, and this term is
called the overlap integral. This represents the electron cloud in the molecular
orbitals. Integral overlap term decides the strength of bond. Larger the value of this
term greater is the bond strength.
The value of N can be evaluated from the equation -3. As probability of finding the
electron in MO is one, the value of integral of eq. 3 should be one.
ʃ [N2(C12ΨA2 + 2C1C2ΨAΨB + C22ΨB2)]dT= 1 ---------- (4)

1
Therefore,N2= -------- (5)
(𝐶12 Ψ21 + 2𝐶1 𝐶2 Ψ𝐴 Ψ𝐵 + 𝐶22 Ψ22 )
By probability, C12ΨA2 = 1, C22ΨB2 = 1 and C1C2ΨAΨB= 0

1
Therefore, N2 = ---- (6)
1+0+1
1
Therefore, N2 =
2
1
and N= ------- (7)
√2
1
Therefore equation -2 become, Ψ = (C1ΨA + C2ΨA) ----------------- (8)
√2
Thus, equation-8 represents linear combination AO’s to form MO’s
Like addition, subtraction of AO’s is possible. This can be represented as follows;
Ψ* = N(C1ΨA - C2ΨB) ----------------- (9)
1
Ψ* = (C1ΨA - C2ΨB) --------------(10)
√2
The Ψ and Ψ* represent two different orbitals. Respectively they are termed as Bonding
MO’s (ABO) and Antibonding MO’s (ABMO). Energies of bonding and antibonding orbitals
are different. (ΨA + ΨA) represents the bonding MO and attractive type of interaction. The sign
of integral overlap (C1C2ΨAΨB) is +ve for this overlap, it means that more electron density is
constructed between the two atomic nuclei. (ΨA - ΨA) represents the formation of anti-bonding
MO and repulsive type of interaction. The sign of integral overlap is -ve (-C1C2ΨAΨB) for this
interaction, it means that less electron density is constructed between the atomic nuclei.
Energy level diagram: The BMO and ABMO have different energies. This is due to
attractive and repulsive type of interactions that results when electrons are present in these
orbitals. BMO energy is less than AO’s as they result into attractive type of interaction. ABMO
energy is more than AO’s as they result into repulsive type of interaction. Total decrease in
energy of BMO is equal to total increase in energy of ABMO. The energy of AOs is distributed
between MO and sum of energy of MO’s is equal to energy of AO’s. The MO energy level
diagram is as shown figure-1. In energy level diagram Y axis represent the energy of orbitals.
The MO energy level diagram represents the relative energies of atomic and MOs.
Figure-1: MO energy level diagram for H2 Molecule
If we consider wave function as sin wave, then it is very simple to understand bonding
and antibonding interactions of AO’s.
i. In bonding interaction two waves interact in phase to construct summative wave.

Figure – 2: In Phase Combination two Ψ (waves) of two ‘H’ AO to from BMO
ii. In antibonding interaction two waves interact out of phase to form destructive wave.
Figure – 3: Out of Phase combination two Ψ of two atoms of ‘H’ to form ABMO
Stabilization Energy: The energy of the bonding molecular orbital is lower than that of the atomic
orbital by an amount ∆ (-∆). This is due to attractive type of interaction and maximum electron density
constructed between to atomic nuclei in BMO’s. This is known as the stabilization energy. The energy of the
antibonding molecular orbital is higher than that of the atomic orbital by an amount ∆ (+∆). Total
stabilization energy can be calculated from the no of electrons filled in to the orbitals.
Total stabilization energy = [(-∆ × e- in BMO) – (+∆ × e- in ABMO)]
If this value is -ve then molecule is formed, if this value is zero than molecule cannot be formed.
For H2 molecule, 2 electrons are filled in bonding

orbitals, while antibonding orbitals are empty.
Therefore, Total stabilization energy =
[(-∆ × e- in BMO) – (+∆ × e- in BMO)]
= [(-∆ × 2e- in BMO) – (+∆ × 0 e- in BMO)]
= - 2∆
For H2 molecule stabilization energy is -2∆.
Therefore, H2 molecule is stable and formed.
The bond dissociation energy of H2 molecule is
434 kJ per mole i.e. 2∆. Thus, BMO is located at -
217kJ per mole in H2 and ABMO at +217 kJ per
mole w.r.t. to AO’s.
Figure: Stabilization energy of MO and ABMO
The energies changes of bonding and antibonding MO’s during bond formation: When
two atom approaches to each other, then energy of system changes as a function of internuclear
distance. The change starts appearing when two atoms are sufficiently close but internuclear
distance is greater than bond distance.

Figure-4: Change in energy of BMO and ABMO with internuclear distance.

i) Energy of BMO’s decreases and have -ve value till internuclear distance is equal to bond
length. At this point BMO’s have minimum energy. As internuclear distance become less than
bond length, energy stat increases. Since below bond distance two positively charged atomic
nuclei become very close to each other and they repel each other strongly (figure-4).
ii) Energy of ABMO’s increases continuously and have +ve value. As internuclear distance
become less than bond length, energy starts increases abruptly since two atomic nuclei become
very close to each other and repel each other strongly. This is shown in figure-4.
2.1 Formation of different types MO’s from AO’s

The valence shell of electron in atoms may consists of s, p, d, and f orbitals. They take
part in bonding i.e. they can form MO’s. The interactions are restricted by two important
characteristics of orbitals;
i) Shape and orientation of the orbital in the space:
ii) Energy of orbital
The orbitals having same orientation (same symmetry) in the space and
having approximately same energy can interact with each other to form MO’s.
We are limiting to ourselves to s and p AO’s. Within this restriction following types of
interactions are possible on the basis of their symmetry properties.
i) s-s combination of orbital
ii) s-p (px, py, pz) combinationof orbital
iii) p-p (px - px, py - py, pz - pz) combination of orbitals
2.1.1. s-s combination of orbital:By considering sign of wave function two
combinations are possible between two s orbitals of different atoms (figure-5)
i) Ψg = ΨA(s) + ΨB(s)or Ψg = - ΨA(s) - ΨB(s)(Ψg Bonding MO)
ii) Ψu = ΨA(s) - ΨB(s)(Ψu Anti-bonding MO)

Figure-5: Shapes of BMO’s and ABMO’s formed from combination of 1s orbitals
(ΨA + ΨB)or (- ΨA - ΨB) represents the in phase interactions of waves of 1s electrons. In

this case +ve lobe of one orbital overlap with +ve lobe of another orbital. Likely -ve lobe of
one orbital overlap with -ve lobe of another orbital. This combination form bonding MO,
where higher electron density is constructed between two atomic nuclei. This is shown in
figure-5. As higher electron density is constructed between two atomic nuclei it results in
attractive type of interaction between two atoms i.e. bonding interaction.
ΨA - ΨB represents the that +ve lobe of one orbital overlap with -ve lobe of another
orbital. This represent interaction of two orbitals out of phase. This combination forms anti
bonding MO, where higher electron density is constructed outside the two atomic nuclei. This
is shown in figure-5. As, less electron density is constructed between two atomic nuclei this
interaction results in repulsive type of interaction between two atoms i.e. ant-bonding
interaction.
2.1.2. s-p combination of orbital: ‘s’ orbital of one atom can overlap with any of the
‘p’ orbital (Px, py and pz) of second atom since s orbital is spherically symmetric in nature. By
considering sign of wave function two combinations are possible between s and p orbitals of
different atoms (figure-6).
i) Ψg = ΨA(s) + ΨB(p)or Ψg = - ΨA(s) - ΨB(p)(Ψg Bonding MO)
ii) Ψu = ΨA(s) - ΨB(p) (Ψu Anti-bonding MO)
(ΨA(s) + ΨB(P))or (- ΨA(s) - ΨB(p)) represents the that +ve lobe of‘2s’orbitalof one atom overlap
with +ve lobe of ‘2p’orbital of second atom. This represent interaction of two orbitals in phase.
Likely -ve lobe of these orbital can overlap with each other. This interaction form bonding MO.
This is shown in figure-6.
ΨA(s) - ΨB(p) represents the that +velobe2s orbital overlap with -ve lobe of2porbital. This
represent interaction of two orbitals out of phase. This combination forms anti bonding MO.
This is shown in figure-6.

Figure-6: Shapes of bonding and antibonding orbitals formed from s-pz orbitals
2.1.3. p-p combination of orbital: ‘p’ orbital of one atom can overlap with any of the
‘p’ orbital of second atom of same orientation. Thus, three different types of interactions are
possible between p orbitals of different atoms. These are px - px, py - py, pz - pz combinations.
One type of p-orbital cannot overlap with another type of p-orbital since their orientations in
space are different in atoms. The orbitals having same orientation in the space can overlap
with each other. (figure-5).The interaction between two similar type of p-orbitals can be
categorized in to two types i) along the internuclear axis (px - px combination) and ii)
perpendicular to internuclear axis (pz–pz and py - py combination) (Note: according to IUPAC
convention z axis is the internuclear axis but many of the reference book use x as internuclear
axis. Thus, according to reference book we have used x axis internuclear axis).
Px orbital of one atom having +ve wave function can overlap with +ve wavefunction of
px orbital of second atom. This interaction take place along the internuclear axis. This is shown
in figure-7. In this interaction maximum electron density is constructed between two atomic
nuclei and along the internuclear axis. This form sigma bonding orbital (σg).
Px orbital of one atom having +ve wave function can overlap with -ve wavefunction of
px orbital of second atom. This interaction take place along the internuclear axis. This is shown
in figure-7. In this interaction maximum electron density is constructed outside the two nuclei
and along the axis. This form sigma antibonding orbital (σu).
Figure-7: Shapes of bonding and antibonding orbitals formed from combination of pz-pz
orbitals
Positive wave function py orbital of one atom can overlap with +ve wavefunction of py
orbital of second atom. This interaction take place perpendicular to the internuclear axis. This

is shown in figure-8. In this interaction maximum electron density is constructed between two
nuclei and below and above the internuclear axis. This form pi (π) bonding orbital (πg).
Figure-8: Shapes of bonding and antibonding orbitals formed from p y-py orbitals
Positive wave function py orbital of one atom can overlap with -ve wavefunction of py
orbital of second atom. This interaction take place perpendicular to the internuclear axis. This
is shown in figure-8. In this interaction maximum electron density is constructed out of two
nuclei and below and above the internuclear axis. This form pi (π) anti-bonding orbital (πu).
Notations σg and σu: The molecular orbital wave functions are designated σg and σu; g stands
for gerade (even) and u for ungerade (odd). g and u refer to the symmetry of the MO’s about
its centre. Rotate the orbital about the line joining the two nuclei and then about a line,
perpendicular to this. If the sign of the lobes remains the same, the orbital is gerade (g), and if
the sign changes, the orbital is ungerade (u).
2.1.4 Non-Bonding Combination of Atomic Orbitals:
When one orbital lobe with +ve sign overlap with another orbital simultaneously with
both lobes (+ve and -ve lobes) of another orbital then this interaction is called non-bonding
interaction. In this combination at a time positive-positive as well as positive -negative overlap
of lobes take place simultaneously and equally. Thus, positive - positive overlap is cancelled by
positive - negative overlap. The net result is no boding as well as antibonding interaction. This
is shown in figure-9 and 10. Non-bonding orbitals in a molecule have same energy as that of
AO in atoms.
Figure-9: Non- bonding combination of s-p orbitals

Figure-10: Non- bonding combination of px -pz orbitals
3. Rules for Linear Combination of Atomic Orbitals:
The rules for linear combination of AO’s to form MO’s can be summarised as follows:
i) Shape and orientation of the orbital in the space: Orbitals taking part in overlap should
have same symmetry around the internuclear axis. the properties of these orbitals should
remain unchanged when rotation is carried out along internuclear axis.
Figure-11: Effect of axial rotation on s and pz orbital
Figure-12: Effect of axial rotation on px and pz orbital
Figure -11 clearly demonstrate that there is no effect of rotation along internuclear axis on
symmetry properties of s and px orbital hence they can overlap with each other. Similar is true for s-py
and s-pz interaction to form sigma bond. However, figure -12 clearly demonstrate the effect of rotation
along internuclear axis on symmetry properties of pz orbitals (lobes are exchanged with each other on
rotation by 180º). But at the same time symmetry properties of px orbitalis not affected. Hence, pz and px
orbitals cannot overlap with each other to form the bond. Likely px-py as well as py-pz overlaps are not
possible.

ii) Energy of orbital: For combination of atomic orbitals of different atoms, theenergy of
orbitals should be approximatively same. E.g. 2s orbitals of Li will not overlap with 3s
orbital of Be since 2s is lower in energy than 3s. however, 2s orbitals of Li can overlap with
2s orbital of Be since they nearly same energy.
iii. The atoms should be at bonding distance so that orbitals can interact with each other to
produce MO’s.
4. Rules for assigning the MO’s and filling of electrons:
i) The MO’s are labelled σ, π,σ* and π*. The subscripts (s, p, sp, etc.) are attached to these
notations of MO’s on the basis of orbitals used for the MO. E.g. 1s-1s combination MO
labelled as σ1s and σ*1s. Likely px-px - asσ2px and σ*2px and py-py - asπ2py and π *2py.
ii) The significance of principal quantum number (n) is same as in electronic configuration of
atoms.
iii) Pauli’s exclusion principle, Aufbau principle and Hund’s rules are applicable for filling of
electrons in MO’s. Thus, i) In one MO, maximum two electrons can be filled with opposite
spin. ii) Electrons are filled according to increasing energy of MO’s. iii) If two or more
MO’s have same energy then, the MO’s are half filled and then pairing of electrons can be
done with opposite spins. Thus, for simple diatomic molecules order of filling of electrons
and increasing energy of orbitals will be as follows;
σ1s< σ*1s< σ2s< σ*2s< σ2px< π2py=π2pz< π*2py=π *2pz< σ*2px, etc.
For lighter elements B and C there is exception that p y and pz orbital become less
energy than 2px orbital. Thus, for these two elements the order of MO’s with increasing
energy will be as follows;
σ1s < σ*1s < σ2s < σ*2s< π2py=π2pz< σ2px < σ*2px< π*2py=π *2pz, etc.
5.Concept of Bond Order and Stabilization Energy:

Number of bonds formed in molecule is called as bond order. It is calculated from electronic
configuration of molecule as follows:
𝑁𝑜𝑜𝑓𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠𝑖𝑛𝐵𝑀𝑂−𝑁𝑜𝑜𝑓𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠𝑖𝑛𝐴𝐵𝑀𝑂
Bond order =
2
Stabilization energy = [(-∆ × e- in BMO) – (+∆ × e- in ABMO)]
Stabilization energy is related to bond order. Stabilization energy increases as bond order increases and
vice a versa is true.
Bond length and bond order: As bond order increases the bond length decreases and vice a versa is
true. When bond order is higher force of attraction between two atoms is higher since more electron
density is constructed between two atomic nuclei. This decreases bond length.
6.Diamagnetic and Paramagnetic Molecules:

The molecule containing unpaired electrons in their MO’s is paramagnetic in nature. The
molecule containing all electrons in paired state in MO’s is diamagnetic in nature.
7. Molecular Orbital Treatment to Simple Homo-diatomic Molecules:
The molecule formed from two atoms of same element is called as homo-diatomic molecule.
Example – H2, N2, O2, F2 etc.
7.1. H2+ molecule ion:
Electronic configuration of H (At. No – 1) is – 1s1 and H+ ion = 1s0
H2+molecular ion can be formed by combination of a H atom with a H+ ion.
The half-filled 1s orbital of H atom combine with empty 1s orbital of H+ ion. This
interaction results into the formation of one σ1s (BMO) and one σ*1s (ABMO) MO’s. The MO
10 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

44
energy level diagram is as shown in figure-13. The one electron occupies σ1s orbital i.e.
configuration is (σ1s)1.
𝟏−𝟎
i. Bond order is = 0.5.
𝟐
ii. Stabilization energy = -∆ + 0 = -∆
iii. The H2+ molecule ion consists of one unpaired e- hence it is paramagnetic in
nature.
H2+ionic molecule is less stable and can be formed under specialized condition only. It
can be formed under reduced pressure in presence of an electric discharge.
Figure – 13: MO energy level diagram of H2+ ion

7.2. H2 molecule:
Electronic configuration of H (At. No.-1) is – 1s1
Thus, H2 molecule is formed by combination of half-filled 1s orbitals of two H atoms.
The half-filled 1s orbital of two H atom combine to form MO’s. This interaction results into the
formation of one σ1s (BMO) and one σ*1s (ABMO) MO’s. The MO energy level diagram is as
shown in figure-14. The two electron occupies σ1s orbital. The configuration of molecule is
(σ1s)2.
𝟐−𝟎
i. Bond order is = 1
𝟐
ii. Stabilization energy = -2∆+0∆ = -2∆
iii. The H2 molecule consists two e-in paired state hence it is diamagnetic in nature.
H2 molecule is highly stable as it consists of one sigma bond between two ‘H’ atoms.

44
Figure – 14: MO energy level diagram of H2molecule

7.3 He2 molecule ion:
+
Electronic configuration of He (At. No.-2) is – 1s2 and He+ is – 1s1

Thus,He2+ molecular ion can be formed by combination of 1s orbitals of one He atoms
and one He+ ion.
The filled 1s orbital of He atom combine with half-filled s orbital of He+ ion to form
MO’s. This interaction results into the formation of one σ1s (BMO) and one σ*1s (ABMO)
MO’s. The MO energy level diagram is as shown in figure-15. The configuration of molecule
is (σ1s)2, (σ*1s)1.
𝟐−𝟏
i. Bond order is = 0.5
𝟐
ii. Stabilization energy = -2∆+∆ = -∆
iii. The He2+ molecular ion consists one unpaired e-hence it is paramagnetic in nature.
He2+ molecular ion is highly unstable as bond order is half. It is formed under
specialized condition and can be detected by spectroscopic methods only.
Figure – 15: MO energy level diagram of He2+molecular ion

7.4. He2 molecule:
Electronic configuration of He (At. No.-2) is – 1s2
He2 molecule can be formed by combination of 1s orbitals of two He atoms.
The filled 1s orbital of two He atom combine to form MO’s. This interaction results
into the formation of one σ1s (BMO) and one σ*1s (ABMO) MO’s. The MO energy level
diagram is as shown in figure-16. The four electron occupies σ1s and σ*1sorbitals. The
configuration of molecule is (σ1s)2, (σ*1s)2.
𝟐−𝟐
𝟐
ii. Stabilization energy = -2∆+2∆ = 0
iii. The bond order in He2 molecule is zero. Therefore, He2 molecule cannot be
formed or its existence is impossible.

44
Figure – 14: MO energy level diagram of He2molecule

7.5. Li2 molecule:
Electronic configuration of Li (At. No.-3) is – 1s2, 2s1
Thus, Li2 molecule can be formed by combination of valence shell 2s orbitals of two Li
atoms. The filled 1s orbital of two Li atom can combine to form MO’s, but essentially this
interaction is absent as they are inner shell orbitals. Therefore, they do not contribute to
bonding in Li2 molecule. Secondly, the half-filled 2s orbital from valence shell of two Li atom
can combine to form MO’s. This interaction results into the formation of one σ2s (BMO) and
one σ*2s (ABMO) MO’s. The MO energy level diagram is as shown in figure-17. Total six
electrons from two Li atoms are filled into MO’s. The configuration of molecule is (σ1s)2,
(σ*1s)2, (σ2s)2
𝟒−𝟐
𝟐
ii) Stabilization energy = -4∆+2∆ = -2∆
iii) The bond order in Li2 molecule is one. Li2 molecule is formed only in gaseous state
and show existence only in gaseous state.
iv) The Li2 molecule consists all e-in paired state hence it is diamagnetic in nature.
Figure – 17: MO energy level diagram of Li2 molecule
7.6. Be2 molecule:

Electronic configuration of Be (At. No.-4) is – 1s2, 2s2
Thus, Be2 molecule can be formed by combination of valence shell 2s orbitals of two
Be atoms. The filled 1s orbital of two Be atom can combine to form MO’s, but essentially this
bonding in Be2 molecule. Secondly, valence shell filled 2s orbital of two Be atom can combine
to form MO’s. This interaction results into the formation of one σ2s (BMO) and one σ*2s
(ABMO) MO’s. The MO energy level diagram is as shown in figure-18. Total eight electrons

44
from two Li atoms are filled into MO’s. The configuration of molecule is (σ1s)2, (σ*1s)2, (σ2s)2,
(σ*2s)2.
𝟒−𝟒
𝟐
ii) Stabilization energy = -4∆+4∆ = 0
iii) The bond order in Li2 molecule is zero. Therefore, Be2 molecule cannot be formed
and do not exists.
Figure – 18: MO energy level diagram of Be2 molecule

7.7. B2 molecule:
Electronic configuration of B (At. No.-5) is – 1s2, 2s2, 2p1
B2 molecule can be formed by combination of valence shell 2s, 2p orbitals of twoB
atoms. The filled 1s orbital of two B atom can combine to form MO’s, but principally this
bonding in B2 molecule. Secondly, valence shell 2s and 2p orbital of two B atom can combine
to form MO’s. This interaction results into the formation of σ2s, σ*2s, π2py π2py, σ2px, σ*2px, π*2py
and π*2pz MO’s. The MO energy level diagram is as shown in figure-19. Total 10 electrons
from two B atoms are to be filled into MO’s. The configuration of molecule is [KK], (σ2s)2,
(σ*2s)2, (π2py)1 (π2pz)1.

44
Figure – 19: MO energy level diagram of B2 molecule

𝟔−𝟒
𝟐
iii) The bond order in B2 molecule is 1. Therefore, B2 molecule can be formed and
exists. However due to Pi bonding the bond strength will be very low. The
molecule can be stabilized as stabilization energy-2∆.
iv) The B2 molecule consists two e-in unpaired state in pi bonding orbitals hence it is
paramagnetic in nature.
7.8. C2 molecule:
Electronic configuration of C(At. No.-6) is – 1s2, 2s2, 2p2
Thus, C2 molecule can be formed by combination of valence shell 2s, 2p orbitals of two
C atoms. The filled 1s orbital of two C atom can combine to form MO’s, but principally this
bonding in C2 molecule. Valence shell 2s and 2p orbital of two C atom can combine to form
MO’s. This interaction results into the formation of σ2s, σ*2s, π2py π2py, σ2px, σ*2px, π*2py and π*2pz
MO’s. The MO energy level diagram is as shown in figure-20. Total 12 electrons from two B
atoms are to be filled into MO’s. The configuration of molecule is [KK], (σ2s)2, (σ*2s)2, (π2py)2
(π2pz)2.

44
Figure – 20: MO energy level diagram of C2 molecule

𝟖−𝟒
𝟐
iii) The bond order in C2 molecule is 2. Therefore, C2 molecule can be formed and
exists. However due to Pi bonding the bond strength will be very low and can be
stabilized as stabilization energy is -ve i.e.-4∆. In fact, carbon exists as a
macromolecule in graphite and diamond. Since these are an even more stable
arrangement (where each carbon forms four bonds): hence diamond and graphite
are formed in preference to C2.
iv) The C2 molecule consists all e-in paired state hence it diamagnetic in nature.
7.9. N2 molecule:
Electronic configuration of N (At. No.-7) is – 1s2, 2s2, 2p3
Thus, N2 molecule can formed by combination of valence shell 2s, 2p orbitals of two N
atoms. The filled 1s orbital of two N atom can combine to form MO’s, but principally this
interaction is absent as they are inner shell orbitals. These orbitals can be considered as non-
bonding orbitals. Valence shell 2s and 2p orbital of two N atoms can combine to form MO’s.
This interaction results into the formation of σ2s, σ*2s, σ2px, π2py π2py, π*2py, π*2pz and σ*2px MO’s.
The MO energy level diagram is as shown in figure-21. Total 14 electrons from two N atoms
are to be filled into MO’s. The configuration of molecule is [KK], (σ2s)2, (σ*2s)2, (σ*2Px)2, (π2py)2
(π2pz)2.

44
Figure – 21: MO energy level diagram of N2 molecule

𝟏𝟎−𝟒
i. Bond order is = 3. Thus, molecule can be represented as N≡N
𝟐
iii) The bond order in N2 molecule is 3. Therefore, N2 molecule can be formed and
must be stable. As such it formed easily and highly stable. The N 2 molecule is
stabilized by stabilization energy of -6∆. Among the three bonds, one sigma and two
are pi bonds. Due to triple bond N2 molecule is highly stable and show very less
reactivity. The reason for inertness of N2 molecule is high energy difference between
pi bonding and pi-antibonding MO’s. To break the bonds the electrons are to be
promoted from Highest Occupied BMO (HOMO) to Lowest Unoccupied ABMO (LUMO).
[In N2 HOMO are π2py, π2pyLUMO are π*2py, π*2pz] the energy difference between
HOMO and LUMO is less molecule is reactive (like that of -C≡C- in alkynes. But if this
energy difference is high then molecule is highly stable like that of N2 molecule.
iv) The N2 molecule consists all e-in paired state hence it diamagnetic in nature.
7.10. O2 molecule:
Electronic configuration of O (At. No.8) is – 1s2, 2s2, 2p4
Thus, O2 molecule can be formed by combination of valence shell 2s, 2p orbitals of two
O atoms. The filled 1s orbital of two O atom can combine to form MO’s, but principally this
bonding orbitals. Valence shell 2s and 2p orbital of two O atoms can combine to form MO’s.
The MO energy level diagram is as shown in figure-22. Total 16 electrons from two O atoms
(π2pz)2, (π2py)1 (π2pz)1.

44
Figure – 22: MO energy level diagram of O2 molecule

𝟏𝟎−𝟔
i. Bond order is = 2. Thus, molecule can be represented as O=O
𝟐
iii) The bond order in O2 molecule is 2. Therefore, O2 molecule can be formed and
must be stable. As such it formed easily and highly stable. The O 2 molecule is
stabilized by stabilization energy of -4∆. Among the two bonds, one sigma and one is
pi bonds.
iv) The O2 molecule consists two e-in unpaired state in pi antibonding orbitals hence it
paramagnetic in nature. Even, practically observed that O2 is paramagnetic
molecule. This is the most successful result of MOT which cannot be obtained
from VBT. The paramagnetic nature of O2 cannot be explained on the basis of Lewis
structure as well as VBT. According to both of these theories O2 is diamagnetic
molecule. However, MOT successfully explained paramagnetic nature of O 2
molecule.
a. O2- (oxygen superoxide) ion: It exists in KO2, NaO2 (i.e. potassium and sodium superoxide)
To formO2-molecular ion one more electron is added in pi antibonding MO of O2
molecule i.e. in all 17 e- to be filled in MO’s. Thus, bond order become;
𝟏𝟎−𝟕
i. Bond order is = 1.5
𝟐
iii)The O2- molecular ion consists one e-in unpaired state in pi antibonding orbitals
hence it paramagnetic in nature.
b. O22- (oxygen peroxide) ion: It exists in Na2O2and H2O2(i.e. sodium and hydrogen peroxide.
To form O22-molecular ion, two more electron is added in pi antibonding MO of O2
molecule i.e. in all 18 e- to be filled in MO’s. Thus, bond order become;
𝟏𝟎−𝟖
𝟐
iii)The O22- molecular ion consists all e-inpaired state hence it diamagnetic in nature.

44
Remember that as electrons are added in ABMO bond order decreases.

Table-1: Comparison of properties of O2 molecule and ions of O2 molecule
O2 Molecule O2- Superoxide ion O22- Peroxide ion O2+ ion
Bond Order 2 1.5 1 2.5
Bond Length (Å) 1.207 1.26 1.49 1.123
-
No of unpaired e 2 1 0 1
Magnetic Property Paramagnetic Paramagnetic diamagnetic Paramagnetic
7.11. F2 molecule:
Electronic configuration of F (At. No.9) is – 1s2, 2s2, 2p5
Thus, F2 molecule can formed by combination of valence shell 2s, 2p orbitals of two F
atoms. The filled 1s orbital of two F atom can combine to form MO’s, but principally this
bonding orbitals. Valence shell 2s and 2p orbital of two F atoms can combine to form MO’s.
The MO energy level diagram is as shown in figure-23. Total 14 electrons from two N atoms
(π2pz)2, (σ*2px)2, (π*2py)2 (π*2pz)2.
Figure – 23: MO energy level diagram of F2 molecule

𝟏𝟎−𝟖
i. Bond order is = 1. Thus, molecule can be represented as F – F.
𝟐
iii) The bond order in F2 molecule is 1. Therefore, F2 molecule can be formed and is
stable. As such it formed easily and highly stable. The F2 molecule is stabilized by
stabilization energy of -2∆. The bond formed is sigma bond.
iv) The F2 molecule consists all e-in paired state hence it diamagnetic in nature.
8. Molecular Orbital Treatment to Simple hetero-diatomic Molecules:

44
The molecule formed from two atoms of different element is called as hetero-diatomic
molecule. Example – HF, NO, CO2, etc.
8.1. HF molecule:
Electronic configuration of H (At. No.1) is – 1s1
Electronic configuration of F (At. No.9) is – 1s2, 2s2, 2p5
Thus, HF molecule can be formed by combination of valence shell orbital of H i.e.1s and
F i.e. 2px orbitals. The half-filled 1s orbital of H atom can combine half-filled 2px orbital of F
atom to form MO’s. Other full filled orbitals of F remain non-bonding. This interaction results
into the formation of σsp and σ*sp, MO’s. The MO energy level diagram is as shown in figure-
24. Two electrons are filled into σsp MO’s.
Figure – 24: MO energy level diagram of HFmolecule

𝟐−𝟎
i. Bond order is = 1. Thus, molecule can be represented as H – F.
𝟐
iii) The bond order in HF molecule is 1. Therefore, HF molecule can be formed and
must be stable. As such it formed easily and highly stable. The HF molecule is
stabilized by stabilization energy of -2∆. The bond formed is sigma bond.
iv) The HF molecule consists two e-in paired state hence it diamagnetic in nature.
Polarity of H-F bond: HF bond is polar in nature. From MO energy level diagram, it is clear
that 2px orbital of F is lower in energy than 1s orbital of H atom. Thus, energetically F atom
orbital is closer to bonding orbital while H atom 1s orbital is energetically closer to antibonding
MO. This affect percent contribution AO’s in bonding and antibonding orbitals. As 2pxorbital
of F atom is energetically close to bonding MO of HF, the electrons in bonding MO lies closer
to F atom i.e. more towards F atom and away from H atom. This induces polar bond character
in H-F bond.
8.2. CO molecule:
Electronic configuration of C (At. No.6) is – 1s1, 2s2, 2p2
The CO molecule can be formed by combination of valence shell orbital of C and O
atoms. The inner shell 1s orbital, both atoms do not take part in bonding i.e. remain non-
bonding. The valence shell orbitals (2s and 2p) of both atoms can combine to form MO’s. This
interaction results into the formation of MO’s as [KK](σ2s)2, (σ*2s)2, (π2py)2 (π2pz)2, (σ2Px)2,

44
(π*2py)0 (π*2pz)0, (σ*2px)0. The MO energy level diagram is as shown in figure-25. Total 10
electrons are filled into these MO’s. Note that AO’s of O are lower in energy than that of C.
Figure – 25: MO energy level diagram of COmolecule

𝟖−𝟐
i. Bond order is = 3. Thus, molecule can be represented as C≡O.
𝟐
iii) The bond order in CO molecule is 3. Therefore, CO molecule can be formed and
must be stable. As such it formed easily and highly stable. The CO molecule is
stabilized by stabilization energy of -6∆. The bond formed are one sigma two pi
bonds.
iv) The CO molecule consists all e-in paired state hence it diamagnetic in nature.
CO+ Ion and Bond order CO+ Ion: CO+ ion is formed by removal of 1 electron from bonding
MO of CO molecule. Thus, we expect that bond order in CO+ will 2.5. Hence one can expect
that bond length in CO+ will increase and should be greater than CO. Practically measured
bond length of CO is 1.128 Å and CO+ is 1.115 Å. This is reverse as expected. Practical
observation indicate that bond length is decreased when we remove one electron to form CO+
ion. This possible only when electron is removed from antibonding MO. Thus, above represent
MO energy level diagram must be somewhat incorrect and should be modified. The energy of
σ*2smust be higher than π2pyand π2pz MO’s (figure-26). Thus, when we remove the electron to
form CO+ ion, it will be removed from σ*2s i.e. antibonding MO and there will be decrease in
number of antibonding electrons. This will result into increase in bond order from 3 to 3.5 and
bond length will decrease as observed. This signifies the need of i) modifying MO energy level
diagrams with the help of practical observation. ii) Furthermore, MO energy level diagrams of
heteronuclear diatomic molecules cannot be drawn as straight forward as drawn for the homo-
diatomic molecules.

44
Figure – 26: Position of σ*2s and π2py, π2pz orbitals in CO
Polarity of CO bond: The bond polarity of CO molecule is interesting. O is electronegative

than C. Note that usually -ve pole in polar molecule lies on more electronegative atom which is
not true in CO. In CO molecule, -ve pole lies on C atom. In this case role is played by
antibonding electrons which acts as lone pair of electrons in CO. This complex situation can be
explained by modifying MO energy level diagram of CO where 2s-2p interactions must be
shown.
8.3. NO molecule:
Electronic configuration of N (At. No.7) is – 1s1, 2s2, 2p3
The NO molecule can be formed by combination of valence shell orbital of N and O
atoms.The inner shell 1s orbital both atoms do not take part in bonding i.e. remain non-
bonding. The valence shell orbitals (2s and 2p) of both atoms can combine to form MO’s. This
interaction results into the formation of MO’s as [KK],(σ2s)2, (σ*2s)2, (π2py)2 (π2pz)2, (σ2Px)2,
(π*2py)1 (π*2pz)0, (σ*2px)0. The MO energy level diagram is as shown in figure-27. Total 11
electrons are filled into these MO’s. Note that AO’s of O are lower in energy than that of N.
Figure – 27: MO energy level diagram of NOmolecule

44
𝟖−𝟑
i. Bond order is = 2.5. Thus, molecule can be represented as N=O.
𝟐
iii) The bond order in NO molecule is 2.5. Therefore, NO molecule can be formed
and must be stable. As such it formed easily, stable but it is reactive. The NO
molecule is stabilized by stabilization energy of -5∆. The bond formed are one
sigma and 1.5 pi bonds.
iv) The NO molecule consists one e-in unpaired state hence it paramagnetic in nature.
Bond order in NO+: NO+ ion is formed by removal of 1 electron from antibonding bonding
MO of NO molecule. The bond order in NO+ is 3 with shorter bond length than NO molecule.

44

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Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

Molecular Orbital Theory of Covalent Bond

1 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

is Linear Combination of Atomic Orbitals (LCAO). It is an approximate solution Schrödinger

ʃ [N2(C12ΨA2 + 2C1C2ΨAΨB + C22ΨB2)]dT= 1 ---------- (4)

By probability, C12ΨA2 = 1, C22ΨB2 = 1 and C1C2ΨAΨB= 0

Figure-1: MO energy level diagram for H2 Molecule

3 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Figure – 2: In Phase Combination two Ψ (waves) of two ‘H’ AO to from BMO

For H2 molecule, 2 electrons are filled in bonding

Figure: Stabilization energy of MO and ABMO

4 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Figure-4: Change in energy of BMO and ABMO with internuclear distance.

2.1 Formation of different types MO’s from AO’s

5 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Figure-5: Shapes of BMO’s and ABMO’s formed from combination of 1s orbitals

(ΨA + ΨB)or (- ΨA - ΨB) represents the in phase interactions of waves of 1s electrons. In

6 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

7 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Figure-9: Non- bonding combination of s-p orbitals

8 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Figure-10: Non- bonding combination of px -pz orbitals

3. Rules for Linear Combination of Atomic Orbitals:

Figure-11: Effect of axial rotation on s and pz orbital

Figure-12: Effect of axial rotation on px and pz orbital

9 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

5.Concept of Bond Order and Stabilization Energy:

6.Diamagnetic and Paramagnetic Molecules:

10 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 13: MO energy level diagram of H2+ ion

11 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 14: MO energy level diagram of H2molecule

Electronic configuration of He (At. No.-2) is – 1s2 and He+ is – 1s1

Figure – 15: MO energy level diagram of He2+molecular ion

12 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 14: MO energy level diagram of He2molecule

Figure – 17: MO energy level diagram of Li2 molecule

7.6. Be2 molecule:

13 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 18: MO energy level diagram of Be2 molecule

14 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 19: MO energy level diagram of B2 molecule

15 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 20: MO energy level diagram of C2 molecule

16 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 21: MO energy level diagram of N2 molecule

17 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 22: MO energy level diagram of O2 molecule

18 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Remember that as electrons are added in ABMO bond order decreases.

Figure – 23: MO energy level diagram of F2 molecule

19 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 24: MO energy level diagram of HFmolecule

20 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 25: MO energy level diagram of COmolecule

21 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

Figure – 26: Position of σ*2s and π2py, π2pz orbitals in CO

Polarity of CO bond: The bond polarity of CO molecule is interesting. O is electronegative

Figure – 27: MO energy level diagram of NOmolecule

22 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

23 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

24 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

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