CHAPTER 1.

Atomic and Molecular Structure

Atomic orbitals (s,p,d,f) orbital shapes, Electronic Configuration, Molecular orbital theory
(MOT), bonding and anti-bonding orbitals, Molecular orbital diagrams of Homonuclear and
Heteronuclear diatomic molecules: Be2, O2, CO, NO their bond order and magnetic properties.

1.1 ATOMIC ORBITAL

In atomic theory and quantum mechanics, an atomic orbital is a mathematical function that
describes the wave-like behavior of either one electron or a pair of electrons in an atom. This
function can be used to calculate the probability of finding any electron of an atom in any
specific region around the atom's nucleus. The term atomic orbital may also refer to the
physical region or space where the electron can be calculated to be present, as defined by the
particular mathematical form of the orbital. Each orbital in an atom is characterized by a
unique set of values of the three quantum numbers n, ℓ, and m, which respectively
correspond to the electron's energy, angular momentum, and an angular momentum vector
component (the magnetic quantum number).
Each such orbital can be occupied by a maximum of two electrons, each with its own spin
quantum number s. The simple names s-orbital, p-orbital, d-orbital and f-orbital refer to
orbitals with angular momentum quantum number ℓ = 0, 1, 2 and 3 respectively. These
names, together with the value of n, are used to describe the electron configurations of
atoms. They are derived from the description by early spectroscopists of certain series
of alkali metal spectroscopic lines as sharp, principal, diffuse, and fundamental. Orbitals for
ℓ > 3 continue alphabetically, omitting j (g, h, i, k, ...) because some languages do not
distinguish between the letters "i" and "j".
Example1.1: How many electrons can s, p, d, f orbital hold?
Answer: If ℓ is the angular quantum number of subshell then maximum electrons it can hold
is 2(2ℓ+1)
Sub-shell ℓ Maximum electrons
s 0 2(2(0)+1)=2
p 1 2(2(1)+1)=6
d 2 2(2(2)+1)=10
f 3 2(2(3)+1)=14
i.e. 2, 6, 10, 14 respectively
1-2 | ENGINEERING CHEMISTRY - I

1.1.1 s, p, d, f ORBITALS
Orbitals are the regions of space in which electrons are most likely to be found. Each orbital
is denoted by a number and a letter. The number denotes the energy level of the electron in
the orbital. Thus 1 refers to the energy level closest to the nucleus; 2 refers to the next energy
level further out, and so on.
The letter refers to the shape of the orbital. The letters go in the order s, p, d, f, g, h, i, k, etc.
Since an electron can theoretically occupy all space, it is impossible to draw an orbital. All
we can do is draw a shape that will include the electron most of the time, say 95% of the
time. We call this shape the 95% contour.
s-ORBITALS
An s orbital is spherically symmetric around the nucleus of the atom, like a hollow ball made
of rather fluffy material with the nucleus at its centre. As the energy levels increase, the
electrons are located further from the nucleus, so the orbitals get bigger. The order of size is
1s < 2s < 3s < …, as shown below.

Now, let’s look at a cross-section of these orbitals.

If you look carefully, you will notice that a 1s orbital has very little electron density near the
nucleus, but it builds up to a maximum as you get further from the nucleus and then
decreases beyond the contour. It is sort of like a hollow tennis ball.
A 2s orbital is similar to a 1s orbital, but it has sphere of electron density inside the outer
sphere, like one tennis ball inside another. There is a surface between the two balls where
there is zero probability of finding an electron. We call this surface a node or a nodal surface.
A 3s orbital is even larger, and it has three nodes.
 ATOMIC AND MOLECULAR STRUCTURE | 1-3

p-ORBITALS
Not all electrons inhabit s orbitals. At the first energy level, the only orbital available to
electrons is the 1s orbital. However, at the second level, there are also orbitals called 2p
orbitals in addition to the 2s orbital. Unlike an s orbital, a p orbital points in a particular
direction.
At any one energy level, we have three absolutely equivalent p orbitals pointing mutually at
right angles to each other. These are arbitrarily given the symbols px, py and pz. This is
simply for convenience, because what you might think of as the x, y or z direction changes
constantly as the atom tumbles in space.
The p orbitals at the second energy level are called 2px, 2py and 2pz. There are similar
orbitals at subsequent levels: 3px, 3py, 3pz, 4px, 4py, 4pz and so on. All levels except the
first have p orbitals.

d-ORBITALS
In addition to s and p orbitals, there are two other sets of orbitals which become available for
electrons to inhabit at higher energy levels. At the third level, there is a set of five d orbitals
(with complicated shapes and names) as well as the 3s and 3p orbitals (3px, 3py, 3pz). At the
third level there are a total of nine orbitals altogether.
1-4 | ENGINEERING CHEMISTRY - I

The five 3d orbitals are called: 3dxy, 3dxz, 3dyz, 3dx²-y² and 3dz²
To make sense of the names, we need to look at them in two groups. The first group contains
the 3dxy, 3dxz and 3dyz orbitals. The names tell you that these orbitals lie in the x-y plane,
the x-z plane, and the y-z plane, respectively. Each orbital has four lobes, and each of the
lobes is pointing between two of the axes, not along them. The second group contains the
3dx² - y² and 3dz² orbitals. Their lobes point along the various axes. The 3dx² - y² orbital
looks exactly like the first group, except that that the lobes are pointing along the x and y
axes, not between them. The 3dz² looks like a p orbital wearing a doughnut around its waist.
f-ORBITALS
At the fourth and higher levels, there are seven f orbitals in addition to the 4s, 4p, and 4d
orbitals.

Counting the 4s, 4p, and 4d orbitals, this makes a total of 16 orbitals in the fourth level. They
have even more complicated shapes. s, p, d, and f orbitals are available at all higher energy
levels as well. Fortunately, you will probably not have to memorize the shapes of the f
orbitals. Just remember that there seven f orbitals in each level from level 4 and onwards.
1.2 ELECTRONIC CONFIGURATION OF ATOMS
The electron configuration of an atom is the representation of the arrangement of electrons
distributed among the orbital shells and subshells. Commonly, the electron configuration is
used to describe the orbitals of an atom in its ground state, but it can also be used to represent
an atom that has ionized into a cation or anion by compensating with the loss of or gain of
electrons in their subsequent orbitals. Many of the physical and chemical properties of elements
can be correlated to their unique electron configurations. The valence electrons, electrons in
the outermost shell, are the determining factor for the unique chemistry of the element.
 ATOMIC AND MOLECULAR STRUCTURE | 1-5

Before assigning the electrons of an atom into orbitals, one must become familiar with the
basic concepts of electron configurations. Every element on the Periodic Table consists of
atoms, which are composed of protons, neutrons, and electrons. Electrons exhibit a negative
charge and are found around the nucleus of the atom in electron orbitals, defined as the
volume of space in which the electron can be found within 95% probability.
The four different types of orbitals (s, p, d and f) have different shapes, and one orbital can
hold a maximum of two electrons. The p, d, and f orbitals have different sublevels, thus can
hold more electrons.
As stated, the electron configuration of each element is unique to its position on the periodic
table. The energy level is determined by the period and the number of electrons is given by
the atomic number of the element. Orbitals on different energy levels are similar to each
other, but they occupy different areas in space.
The 1s orbital and 2s orbital both have the characteristics of an s orbital (radial nodes,
spherical volume probabilities, can only hold two electrons, etc.) but, as they are found in
different energy levels, they occupy different spaces around the nucleus. Each orbital can be
represented by specific blocks on the periodic table.
The s-block is the region of the alkali metals including helium (Groups 1 & 2), the d-block
are the transition metals (Groups 3 to 12), the p-block are the main group elements from
Groups 13 to 18, and the f-block are the lanthanides and actinides series.

Using the periodic table to determine the electron configurations of atoms is key, but also
keep in mind that there are certain rules to follow when assigning electrons to different
orbitals. The periodic table is an incredibly helpful tool in writing electron configurations.
1-6 | ENGINEERING CHEMISTRY - I

1.3 RULES FOR ASSIGNING ELECTRON ORBITALS

1.3.1 THE AUFBAU PROCESS

Aufbau comes from the German word "aufbauen" meaning "to build." When writing electron
configurations, orbitals are built up from atom to atom. When writing the electron
configuration for an atom, orbitals are filled in order of increasing atomic number. However,
there are some exceptions to this rule.
Example 1.2: 3rd row elements
Following the pattern across a period from B (Z=5) to Ne (Z=10), the number of electrons
increases and the subshells are filled. This example focuses on the p subshell, which fills
from boron to neon.
 B (Z=5) configuration: 1s2 2s2 2p1
 C (Z=6) configuration:1s2 2s2 2p2
 N (Z=7) configuration:1s2 2s2 2p3
 O (Z=8) configuration:1s2 2s2 2p4
 F (Z=9) configuration:1s2 2s2 2p5
 Ne (Z=10) configuration:1s2 2s2 2p6
Exceptions
Although the Aufbau rule accurately predicts the electron configuration of most elements,
there are notable exceptions among the transition metals and heavier elements. The reason
these exceptions occur is that some elements are more stable with fewer electrons in some
subshells and more electrons in others
OCCUPATION OF ORBITALS
Electrons fill orbitals in a way to minimize the energy of the atom. Therefore, the electrons
in an atom fill the principal energy levels in order of increasing energy (the electrons are
getting farther from the nucleus). The order of levels filled looks like this:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, and 7p
One way to remember this pattern, probably the easiest, is to refer to the periodic table and
remember where each orbital block falls to logically deduce this pattern. Another way is to
make a table like the one below and use vertical lines to determine which subshells
correspond with each other.
 ATOMIC AND MOLECULAR STRUCTURE | 1-7

1.3.2 PAULI EXCLUSION PRINCIPLE

The Pauli’s exclusion principle states that no two electrons in one atom can have the same
four quantum numbers. The first three (n, l, and ml) may be the same, but the fourth quantum
number must be different. A single orbital can hold a maximum of two electrons, which
must have opposing spins; otherwise they would have the same four quantum numbers,
which is forbidden. One electron is spin up (mS = +1/2) and the other would spin down (mS =
-1/2). This tells us that each subshell has double the electrons per orbital. The s subshell has
1 orbital that can hold up to 2 electrons, the p subshell has 3 orbitals that can hold up to 6
electrons, the d subshell has 5 orbitals that hold up to 10 electrons, and the f subshell has 7
orbitals with 14 electrons.
Example 1.3: Hydrogen and Helium
The first three quantum numbers of an electron are n=1, l=0, ml=0. Only two electrons can
correspond to these, which would be either mS = -1/2 or mS = +1/2. As we already know
from our studies of quantum numbers and electron orbitals, we can conclude that these four
quantum numbers refer to the 1s subshell. If only one of the m s values are given then we
would have 1s1 (denoting hydrogen) if both are given we would have 1s2 (denoting helium).
Visually, this is be represented as:

As shown, the 1s subshell can hold only two electrons and, when filled, the electrons have
opposite spins.
1.3.3 HUND'S RULE
When assigning electrons in orbitals, each electron will first fill all the orbitals with similar
energy (also referred to as degenerate) before pairing with another electron in a half-filled
orbital. Atoms at ground states tend to have as many unpaired electrons as possible. When
visualizing this processes, think about how electrons are exhibiting the same behavior as the
same poles on a magnet would if they came into contact; as the negatively charged electrons
fill orbitals they first try to get as far as possible from each other before having to pair up.
Example 1.4: Oxygen and Nitrogen
If we look at the correct electron configuration of the Nitrogen (Z=7) atom, a very important
element in the biology of plants: 1s2 2s2 2p3

We can clearly see that p orbitals are half-filled as there are three electrons and three p
orbitals. This is because Hund's Rule states that the three electrons in the 2p subshell will fill
all the empty orbitals first before filling orbitals with electrons in them. If we look at the
element after Nitrogen in the same period, Oxygen (Z = 8) its electron configuration is:
1s2 2s2 2p4 (for an atom).
1-8 | ENGINEERING CHEMISTRY - I

Oxygen has one more electron than Nitrogen and as the orbitals are all half filled the electron
must pair up.
1.4 WRITING ELECTRON CONFIGURATIONS
When writing an electron configuration, first write the energy level (the period), then
the subshell to be filled and the superscript, which is the number of electrons in that
subshell. The total number of electrons is the atomic number, Z. The rules above allow one
to write the electron configurations for all the elements in the periodic table. Three methods
are used to write electron configurations:
1. orbital diagrams
2. spdf notation
3. noble gas notation
Each method has its own purpose and each has its own drawbacks.
1.4.1 ORBITAL DIAGRAMS
An orbital diagram, like those shown above, is a visual way to reconstruct the electron
configuration by showing each of the separate orbitals and the spins on the electrons. This is
done by first determining the subshell (s,p,d, or f) then drawing in each electron according to
the stated rules above.
Example 1.5: Write the electron configuration for aluminum.
Solution: Aluminum is in the 3rd period and it has an atomic number of Z=13. If we look at
the periodic table we can see that it is in the p-block as it is in group 13. Now we shall look
at the orbitals it will fill: 1s, 2s, 2p, 3s, 3p. We know that aluminum completely fills the 1s,
2s, 2p, and 3s orbitals because mathematically this would be 2+2+6+2=12. The last electron
is in the 3p orbital. Also another way of thinking about it is that as you move from each
orbital block, the subshells become filled as you complete each section of the orbital in the
period. The block that the atom is in (in the case for aluminum: 3p) is where we will count to
get the number of electrons in the last subshell (for aluminum this would be one electron
because it is the first element in the period 3 p-block). This gives the following:

Note that in the orbital diagram, the two opposing spins of the electron can be visualized.
This is why it is sometimes useful to think about electron configuration in terms of the
diagram. However, because it is the most time consuming method, it is more common to
write or see electron configurations in spdf notation and noble gas notation.
 ATOMIC AND MOLECULAR STRUCTURE | 1-9

1.4.2 spdf NOTATION

The most common way to describe electron configurations is to write distributions in the
spdf notation. Although the distributions of electrons in each orbital are not as apparent as in
the diagram, the total number of electrons in each energy level is described by a superscript
that follows the relating energy level. To write the electron configuration of an atom, identify
the energy level of interest and write the number of electrons in the energy level as its
superscript as follows: 1s2. This is the electron configuration of helium; it denotes a full s-
orbital. The periodic table is used as a reference to accurately write the electron configurations
of all atoms.
Example 1.6: Write the electronic configuration of Yttrium.
Solution: Start with the straightforward problem of finding the electron configuration of the
element yttrium. As always, refer to the periodic table. The element yttrium (symbolized Y)
is a transition metal, found in the fifth period and in Group 3. In total it has thirty-nine
electrons. Its electron configuration is as follows:
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d1
This is a much simpler and more efficient way to portray electron configuration of an atom.
A logical way of thinking about it is that all that is required is to fill orbitals across a period
and through orbital blocks. The number of elements in each block is the same as in the
energy level it corresponds. For example, there are 2 elements in the s-block, and 10
elements in the d-block. Moving across, simply count how many elements fall in each block.
Yttrium is the first element in the fourth period d-block; thus there is one electron in that
energy level. To check the answer, verify that the subscripts add up to the atomic number. In
this case, 2+2+6+2+6+2+10+6+2+1= 39 and Z=39, so the answer is correct.
A slightly more complicated example is the electron configuration of bismuth (symbolized
Bi, with Z = 83). The periodic table gives the following electron configuration:
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p65s2 4d10 5p6 6s2 4f14 5d10 6p3
The reason why this electron configuration seems more complex is that the f-block, the
Lanthanide series, is involved. Most students who first learn electron configurations often
have trouble with configurations that must pass through the f-block because they often
overlook this break in the table and skip that energy level. It is important to remember that
when passing the 5d and 6d energy levels that one must pass through the f-block lanthanoid
and actinoid series. Keeping this in mind, this "complex" problem is greatly simplified.
1.4.3 NOBLE GAS NOTATION
This brings up an interesting point about elements and electron configurations. As the p
subshell is filled in the above example about the Aufbau principle (the trend from boron to
neon), it reaches the group commonly known as the noble gases. The noble gases have the
most stable electron configurations, and are known for being relatively inert. All noble gases
have their subshells filled and can be used them as a shorthand way of writing electron
configurations for subsequent atoms. This method of writing configurations is called the
noble gas notation, in which the noble gas in the period above the element that is being
1-10 | ENGINEERING CHEMISTRY - I

analyzed is used to denote the subshells that element has filled and after which the valence
electrons (electrons filling orbitals in the outer most shells) are written. This looks slightly
different from spdf notation, as the reference noble gas must be indicated.
Example 1.7: What is the electronic configuration of vanadium (V, Z=23)?
Solution: Vanadium is the transition metal in the fourth period and the fifth group. The
noble gas preceding it is argon (Ar, Z=18), and knowing that vanadium has filled those
orbitals before it, argon is used as the reference noble gas. The noble gas in the configuration
is denoted E, in brackets: [E]. To find the valance electrons that follow, subtract the atomic
numbers: 23 - 18 = 5. Instead of 23 electrons to distribute in orbitals, there are 5. Now there
is enough information to write the electron configuration:
Vanadium, V: [Ar] 4s2 3d3
This method streamlines the process of distributing electrons by showing the valence
electrons, which determine the chemical properties of atoms. In addition, when determining
the number of unpaired electrons in an atom, this method allows quick visualization of the
configurations of the valance electrons. In the example above, there are a full s orbital and
three half filled d orbitals.
1.5 INTRODUCTION TO MOLECULAR ORBITAL THEORY
Valence Bond Theory fails to answer certain questions like Why He2 molecule does not exist
and why O2 is paramagnetic? Therefore in 1932 F. Hood and RS. Mulliken came up with
theory known as Molecular Orbital Theory to explain questions like above. According to
Molecular Orbital Theory individual atoms combine to form molecular orbitals, as the
electrons of an atom are present in various atomic orbitals and are associated with several
nuclei.

Fig. 1.1 Molecular Orbital Theory

Electrons may be considered either of particle or of wave nature. Therefore, an electron in an
atom may be described as occupying an atomic orbital, or by a wave function Ψ, which are
solution to the Schrodinger wave equation. Electrons in a molecule are said to occupy
molecular orbitals. The wave function of a molecular orbital may be obtained by one of two
method: 1. Linear Combination of Atomic Orbitals (LCAO). 2. United Atom Method.
 ATOMIC AND MOLECULAR STRUCTURE | 1-11

1.5.1 LINEAR COMBINATION OF ATOMIC ORBITALS (LCAO)

As per this method the formation of orbitals is because of Linear Combination (addition or
subtraction) of atomic orbitals which combine to form molecule. Consider two atoms A and
B which have atomic orbitals described by the wave functions ΨA and ΨB .If electron cloud
of these two atoms overlap, then the wave function for the molecule can be obtained by
a linear combination of the atomic orbitals ΨA and ΨB i.e. by subtraction or addition of wave
functions of atomic orbitals.
ΨMO= ΨA + ΨB
The above equation forms two molecular orbitals
1.5.2 BONDING MOLECULAR ORBITALS
When addition of wave function takes place, the type of molecular orbitals formed are called
Bonding Molecular orbitals and is represented by
ΨMO = ΨA + ΨB.
They have lower energy than atomic orbitals involved. It is similar to constructive interference
occurring in phase because of which electron probability density increases resulting in
formation of bonding orbital. Molecular orbital formed by addition of overlapping of two s
orbitals shown in fig. 1.2. It is represented by 𝜎𝑠 . Energy of Bonding Molecular Orbitals is
less than that of Anti Bonding Molecular Orbitals because the attraction of both the nuclei
for both the electron (of the combining atom) is increased.
1.5.3 ANTI-BONDING MOLECULAR ORBITALS
When molecular orbital is formed by subtraction of wave function, the type of molecular
orbitals formed are called Antibonding Molecular Orbitals and is represented by
ΨMO = ΨA - ΨB
They have higher energy than atomic orbitals involved. It is similar to destructive interference
occurring out of phase resulting in formation of antibonding orbitals.

Fig. 1.2 Formation of Bonding and Anti-Bonding Orbital

1-12 | ENGINEERING CHEMISTRY - I

Molecular Orbital formed by subtraction of overlapping of two s orbitals are shown in fig.
1.2. It is represented by 𝜎𝑠 *, (*is used to represent antibonding molecular orbital) called Sigma
Antibonding. Energy of Anti Bonding Molecular Orbitals is higher than Bonding Molecular
Orbitals because the electrons try to move away from the nuclei and are in repulsive state.
Therefore, Combination of two atomic orbitals results in formation of two molecular orbitals,
bonding molecular orbital (BMO), whereas other is anti-bonding molecular orbital (ABMO).
BMO has lower energy and hence greater stability than ABMO. First BMO are filled then
ABMO starts filling because BMO has lower energy than that of ABMO. Formation of
molecular orbitals occurs by the combination of atomic orbitals of proportional symmetry
and comparable energy. Therefore, a molecular orbital is polycentric and atomic orbital is
monocentric. Number of molecular orbitals formed is equal to the number of atomic orbitals.
1.5.4 ENERGY LEVEL DIAGRAM FOR MOLECULAR ORBITALS
The factors upon which relative energies of molecular orbitals depend are:
(i) Energies of the Atomic orbitals combining to form Molecular Orbitals.
(ii) The extent of overlapping between the atomic orbitals. The greater the overlap, the more
the bonding orbital is lowered and the anti-bonding orbital is raised in energy relative to AOs
The greater the overlap, the more the bonding orbital is lowered and the anti-bonding orbital
is raised in energy relative to atomic orbitals. For e.g., the extent of overlapping in case of 𝜎
- orbital is more than that in 𝜋 - orbital.

Fig. 1.3 Energy Level Diagram for Molecular Orbitals

 ATOMIC AND MOLECULAR STRUCTURE | 1-13

Consequently, the energy of a σ2pz is lower than the energy of bonding π2px or π2py MOs.
Now, 1s atomic orbitals of two atoms form two molecular orbitals designated as σ1s and
σ*1s. The 2s and 2p orbitals (eight atomic orbitals on two atoms) form four bonding
molecular orbitals and four anti-bonding molecular orbitals as:
Bonding MOs: σ2s, σ2p z, π2p x, π2p y
Anti-bonding MOs: σ *2s, σ *2p z, π*2p x , π*2p y
The energy levels of these molecular orbitals have been determined experimentally by
various methods. The order of increasing energy of molecular orbitals obtained by the
combination of 1s, 2s and 2p orbitals of two atoms is:
∗ ∗ ∗ ∗ ∗
𝜎1𝑠 < 𝜎1𝑠 < 𝜎2𝑠 < 𝜎2𝑠 < 𝜎2𝑝𝑧 < 𝜋2𝑃𝑥 = 𝜋2𝑝𝑦 < 𝜋2𝑝𝑥 = 𝜋2𝑝𝑦 < 𝜎2𝑝𝑧

1.5.5 BOND ORDER

It may be defined as the half of difference between the number of electrons present in the
bonding orbitals and the antibonding orbitals that is,
Bond order (B.O.) = (No. of electrons in BMO - No. of electrons in ABMO)/ 2
𝑁𝐵 − 𝑁𝐴
B. O. =
2
1.5.6 ELECTRONIC CONFIGURATION OF THE MOLECULE AND ITS PROPERTIES
1. Stability of molecules in terms of bonding and antibonding electrons: Number of
electrons present in the bonding orbitals is represented by 𝑁𝐵 and the number of
electrons present in antibonding orbitals by 𝑁𝐴 .
(a) If 𝑁𝐵 > 𝑁𝐴 , the molecule is stable because greater number of bonding orbitals are
occupied than antibonding orbital, resulting in a net force of attraction.
(b) If 𝑁𝐵 < 𝑁𝐴 , the molecule is unstable because the antibonding influence is greater
than the bonding influence, resulting in net force of repulsion.
(c) If 𝑁𝐵 = 𝑁𝐴 , the molecule is again unstable because influence of electrons in the
antibonding molecular orbital is greater than the bond influence of electron in the
bonding molecular orbitals.
2. Stability of molecules in terms of bond order: The molecule is stable if 𝑁𝐵 > 𝑁𝐴 i.e.
bond order is positive. The molecule is unstable if 𝑁𝐵 < 𝑁𝐴 i.e. the bond order is
negative or zero.
3. Relative stability of molecule in terms of bond order: For diatomic molecules, the
stability is directly proportional to the bond order. A molecule with the bond order of 3
is more stable than a molecule with bond order of 2 and so on.
4. Nature of bond in terms of bond order: Bond order 1, 2 and 3 mean single, double
and triple bond.
5. Bond length in terms of bond order: Bond length is found to be inversely
proportional to the bond order. Greater the bond order, shorter is the bond length. For
Example the bond length in nitrogen molecule is shorter than in oxygen molecule.
1-14 | ENGINEERING CHEMISTRY - I

6. Diamagnetic and paramagnetic nature of the molecules: If all the electrons in the
molecule are paired (↑↓), it is diamagnetic in nature. If the molecules has some unpaired
electrons (↑), it is paramagnetic in nature. Greater the number of unpaired electrons
present in the molecular or ion, greater is its paramagnetic nature.
1.5.7 DIFFERENCES BETWEEN MOLECULAR ORBITAL AND ATOMIC ORBITAL
Molecular Orbital Atomic Orbital
1. An electron Molecular orbital is under 1. An electron in atomic orbital is under
the influence of two or more nuclei the influence of only one positive
depending upon the number of atoms nucleus of the atom.
present in the molecule.
2. Molecular orbitals are formed by 2. Atomic orbitals are inherent property of
combination of atomic orbitals an atom.
3. They have complex shapes. 3. They have simple shapes.

1.6 MOLECULAR ORBITAL DIAGRAM FOR HOMONUCLEAR DIATOMICS MOLECULES

Molecules consisting of two identical atoms are said to be homonuclear diatomic, such as:
H2, N2, O2, and F2.
1.6.1 MOLECULAR ORBITAL DIAGRAM FOR 𝐁𝐞𝟐 MOLECULE
The electronic configuration of Be (Z = 4) is: 1s2 2s2
Be2 molecule is formed by the overlap of atomic orbitals of both beryllium atoms.
Number of valence electrons in Be atom = 2, thus in the formation of Be molecule, two outer
electrons of each Be atom i.e. 4 in all, have to be accommodated in various molecular
orbitals in the increasing order of their energies.

Fig. 1.4 MO diagram for Be2 Molecule

 ATOMIC AND MOLECULAR STRUCTURE | 1-15

2 ∗ 2
The electronic configuration of Be2 = KK 𝜎2𝑠 𝜎2𝑠
Here KK represents two non bonding 1s orbitals of two Be atoms
𝑁𝐵 − 𝑁𝐴 2 − 2
The B. O. of 𝐵𝑒2 = = =0
2 2
Since bond order is zero, Be molecule does not exist.
Magnetic property: It is diamagnetic due to the absence of any unpaired electron.
1.6.2 MOLECULAR ORBITAL DIAGRAM FOR O2 (DIOXYGEN) MOLECULE
The electron configuration of oxygen (Z=8) is 1s22s22p4. In O2 molecule there are total
sixteen electrons. As 1s orbitals are considered to be non bonding, therefore, four electron of
1s orbitals of both oxygen atom can be ignored and we need to accommodate twelve valence
electrons (six from each oxygen atom) in molecular orbitals.
As you can see from the diagram, this places two electrons in antibonding orbitals. Each of
these electrons occupies a separate π* orbital because this leads to less electron-electron
repulsion (Hund's Rule). The bond energy of molecular oxygen is 498 kJ/mole. This is
smaller than the 945 kJ bond energy of N2- not surprising, considering that oxygen has two
electrons in an antibonding orbital, compared to nitrogen’s one.

Fig. 1.5 MO diagram for O2 Molecule

1-16 | ENGINEERING CHEMISTRY - I

The electronic configuration of O2 molecules can be given as

2 ∗ 2 ∗ 1
∗ 1
𝑂2 = KK 𝜎2𝑠 𝜎2𝑠 𝜎2𝑝𝑧 2 𝜋2𝑝𝑥 2 𝜋2𝑝𝑦 2 𝜋2𝑝𝑥 𝜋2𝑝𝑦
Here KK represents two non bonding 1s orbitals of two O atoms.
𝑁𝐵 − 𝑁𝐴 8 − 4
The Bond Order (B. O. ) of 𝑂2 = = =2
2 2
The two unpaired electrons of the dioxygen molecule give this substance an unusual and
distinctive property: O2 is paramagnetic.
The paramagnetism of oxygen can readily be demonstrated by pouring liquid O 2 between the
poles of a strong permanent magnet; the liquid stream is trapped by the field and fills up the
space between the poles.
Since molecular oxygen contains two electrons in an antibonding orbital, it might be possible
to make the molecule more stable by removing one of these electrons, thus increasing the
ratio of bonding to antibonding electrons in the molecule. Just as we would expect, and in
accord with our model, O2+ has a bond energy higher than that of neutral dioxygen;
removing the one electron actually gives us a more stable molecule. This constitutes a very
good test of our model of bonding and antibonding orbitals.
In the same way, adding an electron to O2 results in a weakening of the bond as evidenced by
the lower bond energy of O2–. The bond energy in this ion is not known, but the length of the
bond is greater, and this is indicative of a lower bond energy. These two dioxygen ions, by
the way, are highly reactive and can be observed only in the gas phase.
1.7 MOLECULAR ORBITAL DIAGRAM FOR HETERONUCLEAR DIATOMICS

Molecules consisting of two non-identical atoms are said to be heteronuclear diatomic, such
as: CO, NO, HF, and LiF.
1.7.1 MOLECULAR ORBITAL DIAGRAM FOR CO MOLECULE
The electronic configuration of carbon and oxygen atom is 1s²2s²2p² and 1s²2s²2p⁴
respectively. As 1s orbitals are considered to be non bonding, therefore, two electron
of 1s orbitals of both oxygen and carbon atom can be ignored. Therefore, there are 4
electrons in the outer shell of carbon and 6 electrons in the outer shell of oxygen. Thus, the
total of 10 outer electrons is to be accommodated in the molecular orbitals of CO molecule.
Because of higher electron negativity of oxygen, its atomic orbitals would be of lower
energy than the corresponding atomic orbitals of carbon.
Due to this energy difference, the bonding and antibonding molecular orbitals will receive
different contributions from atomic orbitals of carbon and oxygen. The bonding molecular
orbitals will receive more contribution from atomic orbitals of lower energy i.e. the atomic
orbitals of Oxygen and would be closer to it in energy than the antibonding molecular
orbitals which would be closer to carbon in energy.
The bonding molecular orbitals would have more characteristics of atomic orbitals of
Oxygen and antibonding Molecular orbitals would have more characteristics of carbon.
 ATOMIC AND MOLECULAR STRUCTURE | 1-17

The electronic configuration of CO molecule is

∗ 2
𝐶𝑂 = KK 𝜎2𝑠 2 𝜎2𝑠 𝜋2𝑝𝑥 2 𝜋2𝑝𝑦 2 𝜎2𝑝𝑧 2
Here KK represents two non bonding 1s orbitals of C and O atoms.
Bond order (B.O.) = (No. of electrons in BMO - No. of electrons in ABMO)/2
𝑁𝐵 − 𝑁𝐴 8 − 2
The Bond Order (B. O. ) of 𝐶𝑂 = = =3
2 2
Thus, CO contains a tripple bond. Its bond dissociation energy is 1067 KJ/mol and bond
length is equal to 1.14Å.Molecular orbital diagram for CO molecule is gven as.

Fig. 1.6 Molecular Orbital Diagram for CO

Magnetic Behavior: If all the molecular orbitals in species are spin paired, the substance is
diamagnetic i.e CO Molecule, it is diamagnetic as all the electron in CO are paired.

1.7.2 MOLECULAR ORBITAL DIAGRAM FOR NO MOLECULE

Nitric oxide (NO) is an example of a heteronuclear diatomic molecule. The reaction of
O2 with N2 at high temperatures in internal combustion engines forms nitric oxide. The
electronic configuration of nitrogen (7) and oxygen (8) atom is 1s2 2s2 2p3 and 1s2 2s2 2p4
respectively and total 15 electron. As 1s orbitals are considered to be non bonding, therefore,
two electron of 1s orbitals of each oxygen and nitrogen atom can be ignored. Therefore, NO
1-18 | ENGINEERING CHEMISTRY - I

has an odd number of valence electrons (5 from nitrogen and 6 from oxygen, for a total of
11), its bonding and properties cannot be successfully explained by either the Lewis
electron-pair approach or valence bond theory.
The molecular orbital energy-level diagram for NO shows that the general pattern is similar
to that for the O2 molecule. Because 10 electrons are sufficient to fill all the bonding
molecular orbitals derived from 2p atomic orbitals, the 11th electron must occupy one of the
degenerate π* orbitals.

Fig. 1.7: Molecular Orbital Energy-Level Diagram for NO.

The electronic configuration of NO molecule is
∗ 2 ∗ 2 ∗ 2
𝑁𝑂 = KK 𝜎2𝑠 2 𝜎2𝑠 𝜋2𝑝𝑥 2 𝜋2𝑝𝑦 2 𝜎2𝑝𝑧 2 𝜋2𝑝𝑥 𝑜𝑟 𝜋2𝑝𝑦
Here KK represents two non bonding 1s orbitals of N and O atoms.
Bond order (B.O.) = (No. of electrons in BMO - No. of electrons in ABMO)/2
𝑁𝐵 − 𝑁𝐴 8 − 3
The Bond Order (B. O. ) of 𝑁𝑂 = = = 2.5
2 2
These values lie between those of the N2 and O2 molecules, which have triple and double
bonds, respectively.
Magnetic Behavior: Since NO has 11 valence electrons, it is paramagnetic, with a single
∗ 2 ∗ 2
electron occupying the (𝜋2𝑝𝑥 or 𝜋2𝑝𝑦 ) pair of orbitals.
 ATOMIC AND MOLECULAR STRUCTURE | 1-19

QUESTIONS
1. Define the term atomic orbitals
2. Explain with diagram, the shapes of 2s and 2p orbitals
3. Write electronic configuration of Hund’s rule.
4. Show the pattern of electrons with configuration of element B to F.
5. Write note on MOT.
6. Define bonding and antibonding orbitals
7. Draw molecular orbital diagram of Be2 and show why it does not exist
8. On the basis of MOT, explain bond order and magnetic behavior or O2
9. Explain in detail the molecular orbital diagram of CO.
10. Draw molecular orbital diagram of NO and explain its bond order and show why it is
less stable than N2.