Atomic Structure: Dept. of Chemistry M. M. Arts and Science College, Sirsi
Atomic Structure: Dept. of Chemistry M. M. Arts and Science College, Sirsi
I sem
(CBCS)
Atomic Structure
• On this account, the numbers used to identify these states are termed
quantum numbers.
• 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,
• 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).
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
orbital, and therefore the angular distribution. The number of angular nodes is equal
• The magnetic quantum number ml determines the number of orbitals and their
• 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
• (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.
• 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).