Agnel Charities

Fr. Conceicao Rodrigues Institute of Technology,Vashi

ATOMIC & MOLECULAR STRUCTURE

Postulates of Bohr’s model

1) There is a small positively charged nucleus surrounded by electrons that travel in circular
orbits around the nucleus.
2) There is a presence of electrostatic forces between the electrons and the nucleus.
3) Electrons revolve around the nucleus in a stationary energy levels called orbits. These orbits
are also known as principal energy levels or shells represented by principal quantum number
‘n’. The shells are represented by letters K,L,M, N and so on.
Limitations
1) It cannot explain chemical bonding of atoms.
2) There is no explanation of distribution of electron within an atom.

1. Shells
 Electrons revolve around the nucleus in a stationary energy levels called orbits.
 These orbits are also known as principal energy levels or shells represented by principal
quantum number ‘n’ which have integral values 1,2,3…and so on.
 The shells are represented by letters K,L,M, N and so on.
 The energy of the shells goes on increasing as the distance of the shell increases from the
nucleus

n Shell Maximum
Number of
Electrons

1 1st Shell (K) 2

2 2nd Shell (L) 8

3 3rd Shell (M) 18

4 4th Shell (N) 32

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Sub-shells
 Shells can be subdivided into subshells. They are designated as s,p,d,f.
 Each subshell in a shell is assigned on Azimuthal Quantum number l. It can have value from
0 to (n-1).
 The maximum number of electron in a given sub shell is given by 2(2I+1)
Shell Sub l Designation of Total Number of
shell subshell Electrons

K s 0 1s 2
L p 1 2s, 2p 8

M d 2 3s, 3p, 3d 18

N f 3 4s, 4p, 4d, 4f 32

Quantum Numbers
The number which identity the state of an electron specify the energy associated with it and its
location around the nucleus are called quantum numbers
1) Principal Quantum Number (n)
Specifies the main energy level (orbit)
2) Azimuthal Quantum Number (l)
Specifies the sub energy level (orbital) and defines the shape of the orbital
3) Magnetic Quantum Number (ml)
Spatial orientations of an orbital
4) Spin Quantum Number (s)
Spin movement of electrons

1) Principle Quantum Number (n)

Total No. of Electrons in an orbit = 2n2
 It defines the distance of electron from the nucleus and its energy level. It has values n=1, 2,
3, 4,….
 They are also represented as K,L,M,N...
 Greater value of n represents bigger orbits with high energies
Value of Name of Total No. of
n Shell Electrons

n=1 K 2(1)2 = 2

n=2 L 2(2)2 = 8
n=3 M 2(3)2 = 18
n=4 N 2(4)2 = 32

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2) Azimuthal Quantum Number (l)

 It represents the sub shell to which the electron belongs.
 It defines the shape of the orbital occupied by the electron and the angular momentum of the
electron
 The value is between 0 and (n-1).

Shell Sub l Designation of Total Number

shell subshell of Electrons

K s 0 1s 2
L p 1 2s, 2p 8
M d 2 3s, 3p, 3d 18
N f 3
4s, 4p, 4d, 4f 32

3) Magnetic Quantum Number (ml)

 The values of m are governed by values of ‘l’. It can have any integral value between –l & +l
through zero. Thus ml = -l,….-2,-1,0,+1,+2,…+l
 For ‘s’ subshell, l=0 Therefore m=0 (s orbital)
 For ‘p’ subshell, l=1 Therefore m=+1,0,-1 (px,py,pz)
 For ‘d’ subshell, l=2 Therefore m= +2,+1,0,-1,-2 (dxy,dyz,dxz,dx2-y2,
dz2 )
 For ‘f’ subshell, l=3 Therefore m=+3,+2,+1,0,-1,-2,-3
(it contains 7 degenerate orbitals)

4) Spin Quantum Number (ms)

 Direction of spin of an electron
 Electron which rotates around the nucleus also rotates around its own axis
 This is called self rotation. Either Clockwise (50%) or anticlockwise (50%)

Atomic orbitals(s,p,d,f) & their shapes:

An orbital is a wave function for an electron defined by the three quantum numbers, n, ℓ,
and ml. Quantum numbers actually come from the solution of the Schrodinger’s wave function
for an electron. What the wave function describes, is a region in space with a particular shape,
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where you are likely to find an electron. In terms of waves, the orbital describes the region in
space where the electron density is very thick. In terms of particles, the orbital describes the
region in space where there is a high probability of finding the electron. The principal quantum
number, n, determines the "size", the azimuthal quantum number, ℓ, determines the "shape" of
the electron wave and the number of nodes in the electron wave, and the magnetic quantum
number, ml, determines the "orientation" of the electron wave.

Quantum mechanics necessitates a fourth quantum number, the spin (s) quantum
number to uniquely designate an electron, ms, could take on two different values – they
were ms = +1/2 and ms = −1/2.

Different electron wave shapes have different names and these names are always letters of the
alphabet like s, p, d, and f. (These letters were chosen on the basis of observations of line
spectra. Certain lines were observed as a "sharp" series; others were classified as "principal",
"diffuse", or "fundamental" series, thus s, p, d, f.) These letters correspond to the shape of the
electron wave, or at least the shape that the electron wave appears to take as a result of its
electron density being thicker in one place than it is in the other.

Shapes of s orbitals:
All ℓ = 0 electron waves are s waves, or waves from the s sublevel, and they all describe
electrons in s orbitals. All electron waves from the s sublevel have the same overall shape- s
orbitals always correspond to spherical waves. The quantum numbers n = 1 and ℓ = 0 describe
a small spherical wave with no nodes, the quantum numbers n = 2 and ℓ = 0 describe a larger
spherical wave with a single node, and the quantum numbers n = 3 and ℓ = 0 describe an even

larger spherical wave with two nodes.

All of these orbitals have ℓ = 0, but they have different values for n. The first orbital has n = 1, and
thus is small and has no nodes. The second orbital has n = 2, and thus is larger and has one node. The
third orbital has n = 3, and thus is even larger and has two nodes.

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Shapes of p orbitals:

All ℓ = 1 electron waves are p waves, or waves from the p sublevel, and they describe electrons in
what are known as p orbitals. Unlike s orbitals, p orbitals are not spherical, so they can have different
orientations in space. Now that all p orbitals have ℓ = 1, how many different p orbital orientations
exist? This can be determined from ml values. (ml is the quantum number associated with the
orientation of a particular orbital).
ml = (2l+1), where ml has values from –l through 0 to +l. So for l=1, ml = -1, 0, +1.
The three different p orbitals (one with ml = −1, another with ml = 0, and the third with ml = 1) turn
out to be perpendicular to each other. In other words, if one p orbital points along the x-axis,another p
orbital points along the y-axis, and the third points along the z-axis.

One interesting property of p orbitals that is different from s orbitals is that the total amount of
electron density changes with both the distance from the center of the atom and the direction.

Shapes of d orbitals:
All ℓ = 2 electron waves are d waves, or waves from the d sublevel, and they describe
electrons in what are known as d orbitals.
For n=3, l may have values of 0,1, 2.
This will give one 3s orbital, three 3p orbitals and five 3d orbitals, corresponding to ml = -2, -1, 0,
1,2. 3d orbitals have different orientations of the angular momentum with respect to z axis. The five
3d orbitals are called 3dxy, 3dxz, 3dyz, 3dx² - y², 3dz²

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Shapes of f orbitals: At the fourth and higher levels, i.e. n=4, l=3, ml= -3, -2, -1, 0, 1, 2, 3. There
are seven f orbitals in addition to the 4s, 4p, and 4d orbitals.

Electronic Configuration

The electronic configuration is the distribution of electrons among the atomic orbitals and
subshells. Applying Aufbau principle, the energy levels are filled up according to which a
maximum of two electrons are put into orbitals in the order of increasing orbital energy. Hund’s
rule is also considered which states that when electrons go into degenerate orbitals(i.e. orbitals
with same energy) they occupy them singly before being paired.

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AUFBAU PRINCIPLE: The aufbau principle, from the German Aufbauprinzip, “to build”
(also called thebuilding-up principle or the aufbau rule) states that in the ground state of an
atom or
ion, electrons fill atomic orbitals of the lowest available energy levels before occupying higher
levels. 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p…………

HUND’S RULE OF MAXIMUM MULTIPLICITY: The rule states that for a given
electron configuration, the lowest energy term is the one with the greatest value of spin
multiplicity. This implies that if two or more orbitals of equal energy are available, electrons
will occupy them singly before filling them in pairs.

PAULI’S EXCLUSION PRINCIPLE: The Pauli Exclusion Principle states that, in an atom or
molecule, no two electrons can have the same four electronic quantum numbers. As an orbital
can contain a maximum of only two electrons, the two electrons must have opposing spins. This
means if one is assigned an up-spin ( +1/2), the other must be down-spin (-1/2).

Molecular Orbital theory:

The Valence Bond Theory fails to answer certain questions like why He2 molecule does not exist
and why O2 is paramagnetic. In 1932 F. Hood and R.S. Mulliken came up with Molecular
Orbital Theory to explain questions like the ones above. The basic postulates of this theory are:

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Fr. Conceicao Rodrigues Institute of Technology,Vashi

1. The electrons in a molecule are present in various molecular orbitals just like electrons of
atoms are present in various atomicorbitals.
2. The atomic orbitals of similar energies and symmetry combine to form molecular orbitals.

3. In an atomic orbital the electron is influenced by one nucleus. In case of molecular orbitals,
the electrons are influenced by multiple atomic orbitals depending on the number of
combining atoms. Hence an atomic orbital is monocentric while a molecular orbital is
polycentric innature.
4. When two atomic orbitals combine, two molecular orbitals are formed, namely bonding
molecular orbital and antibonding molecular orbital.
5. The bonding MO is of lower energy and greater stability than the corresponding antibonding
MO.

6. Electrons fill up the MO following Pauli’s Exclusion principle ((MO can have a maximum
of two electrons and they must have opposite spins), Aufbau (MOs are filled in order of
increasing energies) and Hund’s rules ( pairing of electrons in degenerate orbitals does not
take place till all are half filled) just like atomicorbitals.

According to the Molecular Orbital Theory, individual atoms combine to form molecular
orbitals. Thus the electrons of an atom are present in various atomic orbitals and are associated
with several nuclei.

We know that we can consider electrons as either particle or wave nature. Therefore, we can
describe an electron in an atom as occupying an atomic orbital, or by a wave function Ψ. These
are solutions to the Schrodinger wave equation. Electrons in a molecule occupy molecular
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orbitals. We can obtain the wave function of a molecular orbital by the following methods.

 Linear Combination of Atomic Orbitals (LCAO)

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 the molecule. Consider two atoms A and B
which have atomic orbitals described by the wave functions ΨA and ΨB.

If the electron cloud of these two atoms overlaps, then we can obtain the wave function for the
molecule by a linear combination of the atomic orbitals ΨA and ΨB. The below equation forms two
molecular orbitals.

ΨMO = ΨA + ΨB

The mathematical process of combining atomic orbitals to generate molecular orbitals is

called the linear combination of atomic orbitals (LCAO). The wave function describes
the wavelike properties of an electron. Molecular orbitals are combinations of atomic
orbital wave functions.

Combining waves can lead to constructive interference, in which peaks line up with peaks, or
destructive interference, in which peaks line up with troughs (Figure 2). In orbitals, the waves
are three dimensional, and they combine with in-phase waves producing regions with a higher
probability of electron density and out-of-phase waves producing nodes, or regions of no
electron density.

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Fr. Conceicao Rodrigues Institute of Technology,Vashi

Figure. When in-phase waves combine, constructive interference produces a wave with greater
amplitude. (b) When out-of-phase waves combine, destructive interference produces a wave
with less (or no) amplitude

There are two types of molecular orbitals that can form from the overlap of two atomic s orbitals on
adjacent atoms. The two types are illustrated in Figure. The in-phase combination produces a
lower energy σs molecular orbital (read as “sigma-s”) in which most of the electron density is
directly between the nuclei. The out-of-phase addition (which can also be thought of as subtracting
the wave functions) produces a higher energy molecular orbital(read as “sigma-s-star”)
molecular orbital in which there is a node between the nuclei. The asterisk signifies that the orbital is
an antibonding orbital. Electrons in a σs orbital are attracted by both nuclei at the same time and are
more stable (of lower energy) than they would be in the isolated atoms. Adding electrons to these
orbitals creates a force that holds the two nuclei together, so we call these orbitals bonding orbitals

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Electrons in the orbitals are located well away from the region between the two nuclei. The
attractive force between the nuclei and these electrons pulls the two nuclei apart. Hence, these
orbitals are called antibonding orbitals. Electrons fill the lower-energy bonding orbital before
the higher-energy antibonding orbital, just as they fill lower-energy atomic orbitals before they
fill higher- energy atomic orbitals.

Bonding Molecular Orbitals

When the addition of wave function takes place, the type of molecular orbitals formed are Bonding
Molecular Orbitals. We can represent them by ΨMO = ΨA + ΨB.They have lower energy than
atomic orbitals involved.

Anti-Bonding Molecular Orbitals

When molecular orbital forms by the subtraction of wave function, the type of molecular orbitals
formed are antibonding Molecular Orbitals. We can represent them as ΨMO = ΨA – ΨB. They have
higher energy than atomic orbitals. Therefore, the combination of two atomic orbitals results in the
formation of two molecular orbitals. They are the bonding molecular orbital (BMO) and the anti-
bonding molecular orbital (ABMO).

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Relative Energies of Molecular Orbitals

 Bonding Molecular Orbitals (BMO) – Energy of Bonding Molecular Orbitals is less than
that of Anti Bonding Molecular Orbitals. This is because of the increase in the attraction
of both the nuclei for both the electron (of the combining atom).

 Anti-Bonding Molecular Orbitals (ABMO) – Energy of Anti Bonding Molecular Orbitals is

higher than Bonding Molecular Orbitals. This is because the electron tries to move away
from the nuclei and are in a repulsive state.

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When regions of opposite phase overlap, the destructive wave interference decreases electron
density and creates nodes. When p orbitals overlap end to end, they create σ and σ* orbitals.

If two atoms are located along the x-axis in a Cartesian coordinate system, the two px orbitals
overlap end to end and form σpx (bonding) and (antibonding) (read as “sigma-p-x” and
“sigma-p- x star,” respectively). Just as with s-orbital overlap, the asterisk indicates the orbital

with a node between the nuclei, which is a higher-energy, antibonding orbital.

Figure. Combining wave functions of two p atomic orbitals along the internuclear axis
creates two molecular orbitals, σp and σ*p.

The side-by-side overlap of two p orbitals gives rise to a pi (π) bonding molecular orbital and
a π* antibonding molecular orbital, as shown in Figure . In valence bond theory, we describe
π bonds as containing a nodal plane containing the internuclear axis and perpendicular to the

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lobes of the p orbitals, with electron density on either side of the node. In molecular orbital
theory, we describe the π orbital by this same shape, and a π bond exists when this orbital
contains electrons. Electrons in this orbital interact with both nuclei and help hold the two atoms
together, making it a bonding orbital. For the out-of-phase combination, there are two nodal
planes created, one along the internuclear axis and a perpendicular one between the nuclei.

Figure 5. Side-by-side overlap of each two p orbitals results in the formation of two π
molecular orbitals.

Combining the out-of-phase orbitals results in an antibonding molecular orbital with two
nodes. One contains the internuclear axis, and one is perpendicular to the axis. Combining the
in-phase orbitals results in a bonding orbital. There is a node (blue) containing the internuclear
axis with the two lobes of the orbital located above and below this node.

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In the molecular orbitals of diatomic molecules, each atom also has two sets of p orbitals
oriented side by side (py and pz), so these four atomic orbitals combine pairwise to create two π
orbitals and two π* orbitals. The πpy and orbitals are oriented at right angles to the πpz
and orbitals. Except for their orientation, the πpy and πpz orbitals are identical and have the
same energy; they are degenerate orbitals. The and antibonding orbitals are also
degenerate and identical except for their orientation. A total of six molecular orbitals results
from the combination of the six atomic p orbitals in two atoms: σpx and , πpy and ,
πpzand .

Molecular Orbital Energy Diagram

In the molecular orbital model, an electron contributes to a bonding interaction if it

occupies a bonding orbital and it contributes to an antibonding interaction if it occupies an
antibonding orbital. The bond order is calculated by subtracting the destabilizing (antibonding)
electrons from the stabilizing (bonding) electrons. Since a bond consists of two electrons, we
divide by two to get the bond order. We can determine bond order with the following equation:

The order of a covalent bond is a guide to its strength; a bond between two given atoms
becomes stronger as the bond order increases. If the distribution of electrons in the molecular
orbitals between two atoms is such that the resulting bond would have a bond order of zero, a
stable bond does not form.
electrons from two Be atoms to be filled in the MO. The 1s orbital of
MO diagram of Be2 both the Be atoms do not take part in the bond formation i.e. they are

The electronic non bonding. The remaining 2s orbitals of the two Be atoms combine

configuration of Be2 is to form σ2s (bonding) and σ*2s (antibonding) MO. The four

1s2, 2s2. In a diatomic electrons will be filledin both these as per Aufbau principle as shown.

molecule Be, there will The bond order of Be2 is 1s2, 2s2

be a total of eight

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Electronic configuration
σ1s2, σ*1s2, σ2s2, σ*2s2

Bond order = (No of bonding electrons – No. of antibonding electrons) = (4-4) = 0

2 2

The zero bond order means Be2 molecule does not exist.

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MO Diagram of O2
The electronic configuration of O2 is 1s2, 2s2, 2p4. Each oxygen has eight electrons. Hence in O2
molecule, there are 16 electrons. As 1s orbitals are considered to be non bonding, the four electrons
of 1s orbital of both the oxygen atom can be ignored. It is paramagnetic.
Now there are 12 electrons in all to be filled in molecular orbitals. As per Aufbau principle, the next
four occupy σ2s (bonding) and σ*2s (antibonding) MO. The remaining 8 electrons occupy 2p orbital

Electronic configuration of O2 :
KK, σ2s2, σ*2s2, σ2px2, (π2py2= π2pz2), (π*2py1=π*2pz1),σ*2px0

Bond order = (N of e- in bonding – N of e- in antibonding)

2
= (8-4)
2
=2
Therefore, double bond is formed

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Bonding in Heteronuclear Diatomic Molecules

NO
Electronic configuration of the constituent atoms are:

N7- 1s22s22p3

O8- 1s22s22p4

Because NO has an odd number of valence electrons (7 from nitrogen and 8 from oxygen, for a
total of 15), the molecular orbital energy-level diagram for NO shows that the general pattern is
similar to that for the O2 molecule.

The electronic configuration of the molecule is:

KK, σ2s2, σ*2s2, σ2px2, (π2py2= π2pz2), (π*2py1=π*2pz0),σ*2px0

Because 14 electrons are sufficient to fill all the bonding and antibonding molecular orbitals
derived from 1s, 2s and bonding MO of 2p atomic orbitals, the 15th electron must occupy one of
the degenerate π* orbitals.
NO has 10 electrons in bonding MOs and 5 electrons in antibonding MOs. The predicted bond order
for NO is therefore (8-3) ÷ 2 = 2.5 .

Experimental data, showing an N–O bond length of 115 pm and N–O bond energy of 631 kJ/mol,
are consistent with this description. These values lie between those of the N2 and O2 molecules,
which have triple and double bonds, respectively. The molecular orbital theory can therefore
explain the bonding in molecules with an odd number of electrons, such as NO, whereas Lewis
electron structures cannot.

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Figure : Molecular Orbital Energy-Level Diagram for NO.

It is paramagnetic.

Molecular orbital theory can also tell us something about the chemistry of NO. As indicated in
the energy-level diagram in Figure NO has a single electron in a relatively high-energy
molecular orbital. We might therefore expect it to have similar reactivity as alkali metals such as
Li and Na with their single valence electrons. In fact, NO is easily oxidized to the NO+ cation,
which is isoelectronic with N2 and has a bond order of 3, corresponding to an N≡O triple bond.

CO- Heteronuclear diatomic molecule.

The atomic configurations of the constituent atoms are:

C6- 1s22s22p2 O8- 1s22s22p4

The total number of electrons in the CO molecule are 14.

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Hence CO has 8 electrons in the bonding MOs and 2 electrons in the antibonding MOs. So its
B.O. = (8-2) /2 =3
Electronic configuration
KK, σ2s2, σ*2s2, (π2py2= π2pz2), σ2px2, (π*2py0 =π*2pz0),σ*2px0

Since there are no unpaired electrons in the valence shell of CO, it exhibits diamagnetic behavior

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