Quantum Numbers

QUANTUM NUMBERS
Bohr had a single quantum number, n, to describe the energy levels in hydrogen .The quantum mechanical model
uses three quantum numbers, n, l, and ml to describe an orbital.
n is the principal quantum number. It is given values of 1, 2, 3, ... It determines the overall size of the orbital
and energy of the electron. As n increases, the orbitals become larger, and the electron spends more time farther
away from the nucleus. The further an electron is from the nucleus, the less tightly bound it becomes. For
hydrogen-like systems, the quantum mechanical calculation of energy becomes exactly the same as the equation
developed by Bohr.
l is the angular momentum quantum number. It has values of 0, 1, 2, ..., (n-1) for any value of n. It determines
the shape of the orbital. These are usually designated by letters:
l=0 s
l=1 p
l=2 d
l=3 f
m is the magnetic quantum number. It is given values between l and -l. It determines the orientation of the
l
orbital in space.
Orbitals with the same principal quantum number, n, are in the same electron shell.
Orbitals with the same principal quantum number, n and the same angular momentum quantum number, l,
are in the same subshell.
For n = 4, the allowed subshells and number of orbitals are
If n = 4, l = 0, 1, 2, 3
l = 0 = 4s subshell
l = 1 = 4p subshell
l = 2 = 4d subshell
l = 3 = 4f subshell
In the 4s subshell, l = 0 so m = 0 and there is 1 orbital
l
In the 4p subshell, l = 1 so m = -1, 0, +1 and there are 3 orbitals

l
In the 4d subshell, l = 2 so m = -2, -1, 0, +1, +2 and there are 5 orbitals

l
In the 4f subshell, l = 3 so m = -3, -2, -1, 0, +1, +2, +3 and there are 7 orbitals
l
The Spin Quantum Number, ms

A Dutch physicist, Pieter Zeeman, discovered that the atomic emission spectral lines are split into multiple lines
when an magnetic field is applied. These additional lines cannot be accounted for by just the three quantum
numbers, n, l and ml. Two other Dutch physicists, Samuel Goudsmit and George Uhlenbeck, suggested that a
fourth quantum number would be necessary to explain these findings. This number takes into account the
magnetic properties of electrons. Electrons possess a magnetic moment, and can exist in one of two states, spin
up ↑, or spin down ↓. The quantum numbers associated with this are ms = + ½ and ms = - ½ . Wolfgang Pauli, an
Austrian physicist, stated that in a given atom, no two electrons can have the same four quantum numbers.
This is called the Pauli Exclusion Principle. Two electrons occupying the same orbital must have different spin
states↑ (↓). They are said to be paired electrons. This fourth quantum number is not included in the Schrödinger
equation. However, Dirac's treatment predicted the necessity of a fourth quantum number.
It is the magnetic moment associated with electron spin that gives all substances their magnetic properties.
Substances with all of their electrons paired are slightly repelled by magnetic fields and are said to be
diamagnetic. Substances with electrons that have unpaired spins are attracted to magnetic fields and are said
to be paramagnetic.
Orbital shapes and Energies
s orbitals
l=0
All s orbitals are spherical. The relative sizes of the 1s, 2s and 3 s orbitals are shown below. These figures
represent, the boundary surfaces of these orbitals, the volume which contains 90% of the electron density.
In cross section, the nodes in the 2 and 3 s orbitals

are visible.
p orbitals
l=1
The principal quantum number n = 1 can only have l = 0 and no p orbitals. For n = 2, l = 0 and 1, so ml = -1, 0
and 1. These are the three p orbitals.
Shown below are the boundary surfaces of the three 2p orbitals, 2px, 2py and 2pz.
Except for their differing orientations, these orbitals are identical in shape and energy. The p orbitals of higher
principal quantum numbers have similar shapes.
d orbitals
l=2
The principal quantum number n = 3 is the first that that can have d orbitals: ml = -2, -1, 0, 1, 2. These are
shown below.
The different orientations correspond to the different values of m . All five orbitals have identical energy . The d
l
orbitals for n > 3 have similar shapes. Because of the shapes and orientations of the p and d orbitals, electrons
occupying different atomic orbitals are as far apart from each other as possible. This minimizes the electron-
electron repulsion. Beyond the d orbitals, there are f and g etc. orbitals. The f orbitals are important in
accounting for the behavior of elements bigger than Cerium ( > 58), but their orbital shapes are difficult to
represent.
ZEEMAN AFFECT
The experimental arrangement to study Zeeman affect is shown in the Fig(a).
An electromagnetic MM capable of producing a very strong magnetic field
and having conical pole-pieces PP, through which holes have been drilled
lengthwise to view spectral lines. A source L emitting spectral lines is placed
between the pole pieces. The spectral lines are observed with a high
resolving power instrument in conjunction with spectrometer S.
Viewing the spectral line longitudinally through the hole drilled in the pole
pieces and hence parallel to the direction of the field and on establishing the
magnetic field the line is found to split up into two(doublet), one having
slightly shorter wavelength and the other is slightly greater than that of the
original line which no longer seen. The components that appear whenever
the field is are found to be symmetrically situated about the position of
original line so that change in the frequency dν known as Zeeman shift is
same in both the cases. Analyzing the nature of the polarization of the lines,
they are found to be circularly polarized in opposite directions as shown by
the arrows above the line(Fig-b). When viewed transversely i.e.
perpendicular to the direction of the magnetic field the line become a triplet
in which the central having the same wavelength as the original line and
outer one occupies same position as the doublet in the longitudinal case as
shown in (Fig-b).
The splitting is associated with the orbital angular momentum quantum number L of the atomic level. This quantum number
can take non-negative integer values. The number of split levels in the magnetic field is 2L + 1.
The spectrum shows L=1 ("p" level), so it is splited into 2L + 1 = 3 levels by the magnetic field. Thus, a single transition is
split into 3 transitions by the magnetic field.
The Zeeman affect can be interpreted in terms of the precession of the orbital angular momentum vector in the magnetic field,
similar to the precession of the axis of a spinning top in a gravitational field.

Quantum Numbers

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QUANTUM NUMBERS

In the 4p subshell, l = 1 so m = -1, 0, +1 and there are 3 orbitals

In the 4d subshell, l = 2 so m = -2, -1, 0, +1, +2 and there are 5 orbitals

The Spin Quantum Number, ms

In cross section, the nodes in the 2 and 3 s orbitals

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