Atomic Structure: Dept. of Chemistry M. M. Arts and Science College, Sirsi

B. Sc.
I sem
(CBCS)
Atomic Structure
Dr. Divya Hegde

Dept. of Chemistry
M. M. Arts and Science College, Sirsi
Contents
• Review of Bohr’s theory and its limitations,
• Dual behavior of matter and radiation,
• De-Broglie relation. Heisenberg Uncertainty principle.
• Hydrogen atom spectra. Need of a new approach to Atomic structure.
• What is quantum mechanics? Time independent .
• Schrodinger equation and meaning of various terms in it.
• Significance of ѱ and ѱ2, Schrodinger equation for hydrogen atom.
• Radial and angular parts of the hydogenic wave functions (atomic orbitals) and their
variations for 1s, 2s, 2p, 3s, 3p and 3d orbitals (graphical representation).
• Radial and angular nodes and their significance.
• Radial distribution functions and the concept of the most probable distance with special
reference to 1s and 2s atomic orbitals.
• Significance of Quantum Numbers, orbital angular momentum and quantum numbers ml and
ms.
• Shapes of s. p and d atomic orbitals, nodal planes.
• Discovery of spin, spin quantum number (s) and magnetic spin quantum number (ms).
• Rules for filling electrons in various orbitals, Electronic configuration of atoms.
• Stability of half filled and completely filled orbitals, concept of exchange energy.
• Relative energies of atomic orbitals, Anamolous electronic configurations.
Quantum numbers (n, l, m) and its Significance:
• An electron in an atom has some location relative to the nucleus and is

associated with some energy.
• These properties taken together describe the state of t he electron are

governed by the laws of quantum mechanics.
• On this account, the numbers used to identify these states are termed
quantum numbers.
• They specify the location and the energy of an electron.
• Each electron is characterized by four quantum number- the Principal,

Azimuthal, Magnetic and Spin quantum numbers.
Principal quantum number (n):
• It specifies the location and energy of an electron and is a measure of the
effective volume of the electron cloud.
• As the value of n increases, i.e., energy levels get further away from the
nucleus, the value of E increases or becomes less negative.
• The principal quantum number , n=1, represents the energy level nearest to
the nucleus, n=2 is the next energy level further from the nucleus, and
2,3,4, etc are also designated by letters K,L,M,N, etc.
Azimuthal/subsidiary/orbital quantum number (l) :
• Each shell is made up of sub-shells in a shell is given by its principal quantum number. Thus
K or 1-shell has only one subshell. L or 2-shell has two sub-shells, M or 3-shell has 3 sub-
shells. These sub-shells differ from one another in their azimuthal signed l values 0,1,2,..(n-1).
It determines the shape of the orbital (electron cloud) i.e., whether the cloud is spherical,
dumb-bell shaped or has some more complicated shape.
• Values of l (=0,1,2 and 3) are usually represented by the letter s, p, d and f respectively. These
letters are the initial letters of the words, sharp, principal, diffuse and fundamental, the terms
used to describe series of lines observed in atomic spectra. When more than one electron are
present, the energy of a particular electron is determined not only by the value of n, p
electrons have slightly more energy than the s electrons. Similarly, d electrons have slightly
higher energy than p electrons and energy of f electron is slightly higher than that of d
electrons.
Discovery of spin, spin quantum number (s) and magnetic spin quantum
number (ms).
• The concept of spinning electron was introduced by Uhlenbeck and

Goudsmit. It is integral value ½. It actually measures the angular
momentum of the electron due to its spinning motion. In magnetic field it
has got only two quantized orientations giving rise to the magnetic spin
quantum numbers which is given by +1/2 and -1/2.
Spin quantum numbers (s): It indicate the direction in which the electron is
spinning clockwise or anti-clockwise. Clockwise spin is represented by an
arrow pointed upwards while anti-clockwise spin is represented by an arrow
pointing downwards. The allowed spin quantum numbers are only +1/2 and -
1/2. An orbital can accommodate two electrons provided they have
opposite spins.
Significance of quantum numbers:
• The principal quantum number, n, designates the principal electron shell. Because n
describes the most probable distance of the electrons from the nucleus, the larger
the number n is, the farther the electron is from the nucleus, the larger the size of
the orbital, and the larger the atom is.
• The orbital angular momentum quantum number l determines the shape of an
orbital, and therefore the angular distribution. The number of angular nodes is equal
to the value of the angular momentum quantum number l.
• The magnetic quantum number ml determines the number of orbitals and their
orientation within a subshell.
• Unlike n, l, and ml, the electron spin quantum number ms does not depend on
another quantum number. It designates the direction of the electron spin and may
have a spin of +1/2,-1/2.

Shapes of s, p and d orbitals
based on radical probability distribution curve
Shapes of s-orbital:
• For s-orbitals, l=0 and m=0.
• This shows that s-orbitals have only one orientation. It is possible only when s-orbitals
are spherical.
• S-orbitals donot have directional character.
• The size of s-orbitals depends on the value of its principal quantum number (n). Greater
is the value of n, largern is the size of the orbital.
• Thus energy and size of s-orbitals increases in the order 1s<2s<3s<4s….
• The orbital wave function Ѱ for an electron in an atom has no physical meaning. But the
plots of Ѱ as a function of r are different for different orbitals as shown for 1s and 2s
orbitals.
• The variation of Ѱ2 as a function of r for 1s and 2s orbitals are shown in the
following diagram.
• (a) Variation of orbital wave function Ѱ with distance (r) of the electron
from the nucleus (b) variation of probability density Ѱ2 with distance (r)
• Description of the curves: The probability of electron in 1s orbital is
found to be maximum near the nucleus increases. For 2ss electrons also the
probability is maximum near the nucleus. It then decreases to zero and then
increases to a maximum and then decreases as the distance from the
nucleus increases. The region where the probability is zero is called nodal
surface or simply nodes.
• Node also represents the point where the wave function Ѱ changes its sign
i.e., from + to -. 1s orbital has no node whereas 2s orbital has one node.
• The shapes of s-orbitals may also be explained in the following 2 ways-
• In case of s-orbitals, the probability of finding the electron at a given

distance (r) from the nucleus is found to be identical in all directions. This
shows that s-orbital is spherical which is symmetrical around the nucleus.
• For s-orbitals, l=0 and m=0. This shows that s-orbitals are have only one
orientation. It is possible only when s-orbitals are spherical. S-orbital
donot have directional character.
Shape of p-orbitals:
• It has been found that the probability of finding the p-electrons is maximum
in 2 lobes on the opposite sides of the nucleus.
• The probability density function is zero on the plane where the 2 lobes
touch each other.
• The size, shape and energies of three p-orbitals are identical. They differ
only in their orientation.
Shape of p-orbitals:
• For p-orbital l=1 and m=+1,0,-1. Thus p-orbitals have three different
orientations which are designated as px, py and pz. The electron density in
px, py and pz orbitals is maximum along X-, Y- and Z- axis respectively.
Thus p-orbitals have directional character. Greater is the value of n,
larger is the size of p-orbital. The energy and size of p-orbitals increases in
the following order: 2p<3p<4p<5p…
• For a given principal quantum number (n), the orbitals px,py and pz have
equal energies. Such orbitals are called degenerate.
• Spherical nodal planes: their number is given by n –l -1. For p-orbitals l=1.
Thus numbers of spherical nodal planes for 2p, 3p and 4p orbitals are 0, 1
and 2 respectively.
Shape of d-orbitals:
Shape of d-orbitals:
• For d-orbitals l=2 and m=+2,+1,0,-1,-2. Thus there are 5 possible
orientations of electron cloud. These are designated as dx2-y2, dxz, dz2, dyz,
dxy. For a given shell these 5 orbitals have equal energy and are called
degenerate. In dxy, dxz and dyz orbitals, the lobes lie between X and Y, X and
Z, Y and Z axis. The dz2 orbital has 2 lobes which lie along Z-axis and a
ring of high electron density lies in XY plane.
• Spherical nodal planes: Their number is given by n-l-1. For d-orbitals l=2.
The number of spherical nodal planes for 3d, 4d and 5d orbitals is 0,1 and 2
respectively.
• Angular nodes: Besides spherical (radial) nodes, there are angular nodes
also where the probability density functions are zero. For ex:, in case of pz
orbital, XY plane is a nodal plane. In case of dxy orbital, there are 2 nodal
planes passing through the origin and bisecting the XY plane containing Z-
axis. These are called angular nodes and their number is equal to the
Azimuthal quantum number (l).

Atomic Structure: Dept. of Chemistry M. M. Arts and Science College, Sirsi

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B. Sc.

Dr. Divya Hegde

• An electron in an atom has some location relative to the nucleus and is

• These properties taken together describe the state of t he electron are

• They specify the location and the energy of an electron.

• Each electron is characterized by four quantum number- the Principal,

dumb-bell shaped or has some more complicated shape.

• The concept of spinning electron was introduced by Uhlenbeck and

the orbital, and the larger the atom is.

• The orbital angular momentum quantum number l determines the shape of an

to the value of the angular momentum quantum number l.

orientation within a subshell.

have a spin of +1/2,-1/2.

• The shapes of s-orbitals may also be explained in the following 2 ways-

• In case of s-orbitals, the probability of finding the electron at a given

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