2 Atomic Structure
2 Atomic Structure
2 Atomic Structure
“Atomic Structure”
HISTORY OF THE ATOM
ATOMS
HISTORY OF THE ATOM
an
ELECTRON
In 1897, J.J. Thomson used a cathode ray
tube to deduce the presence of a negatively
charged particle: the electron
1. The cathode rays start from cathode and
move towards the anode.
me = e/(e/me)
= 9.1094×10–31 kg
Electrical discharge carried out in the modified
cathode ray tube led to the discovery of
particles carrying positive charge, also known
as canal rays.
the positively charged particles depend upon
the nature of gas present in the cathode ray
tube. These are simply the positively charged
gaseous ions.
The charge to mass ratio of the particles is
found to depend on the gas from which these
originate.
Some of the positively charged particles carry
a multiple of the fundamental unit of electrical
charge.
The behaviour of these particles in the
magnetic or electrical field is opposite to that
observed for electron or cathode rays.
The smallest and lightest positive ion was
obtained from hydrogen and was called
proton.
Eugen Goldstein in 1886 observed
what is now called the “proton” -
particles with a positive charge, and
a relative mass of 1 (or 1840 times
that of an electron)
1932 – James Chadwick confirmed
the existence of the “neutron” – a
particle with no charge, but a mass
nearly equal to a proton
Particle Absolute Relative Mass (g)
Charge Charge
Electron -1.6022x10-19 -1 9.11 x 10-28
(e-)
Conclusions:
a) The nucleus is small
b) The nucleus is dense
c) The nucleus is positively
charged
Based on his experimental evidence:
• The atom is mostly empty space
• All the positive charge, and almost all the
mass is concentrated in a small area in
the center. He called this a “nucleus”
• Size of the nucleus is very very small.
The positive charge and most of the mass of
the atom is concentrated in extremely small
region, called nucleus.
The nucleus is surrounded by electrons that
move around the nucleus with a very high
speed in circular paths called orbits.
Electrons and the nucleus are held together by
electrostatic forces of attraction.
When an electron is moving in an orbit, it
undergoes acceleration (because of changing
direction). According to the electromagnetic
theory of Maxwell, charged particles when
accelerated should emit electromagnetic
radiation
Therefore an electron in an orbit will emit
radiation and as a result the radius of orbit will
continue to shrink. This may lead to the falling
of electron into the nucleus. But this does not
happen. Thus, the Rutherford model cannot
explain the stability of an atom.
This model also failed to explain the
arrangement of electrons around the nucleus.
Atomic number (Z) of an element is
the number of protons in the nucleus
of each atom of that element.
Element # of protons Atomic # (Z)
Carbon 6 6
Phosphorus 15 15
Gold 79 79
Mass number is the sum of protons
and neutrons in the nucleus of an
isotope: Mass # = p+ + n0
Nuclide p+ N0 e- Mass #
Oxygen - 18 8 10 8 18
Arsenic - 75 33 42 33 75
Phosphorus - 31 15 16 15 31
Contain the symbol of the element,
the mass number and the atomic
number.
Superscript →
Mass
X
number
Subscript →
Atomic
number
Dalton was wrong about all
elements of the same type being
identical
Atoms of the same element can
have different numbers of
neutrons.
Thus, different mass numbers.
These are called isotopes.
Frederick Soddy (1877-1956)
proposed the idea of isotopes in
1912
Isotopes are atoms of the same element
having different masses, due to varying
numbers of neutrons.
Soddy won the Nobel Prize in Chemistry
in 1921 for his work with isotopes and
radioactive materials.
Isotopes are atoms of the same element having
different masses, due to varying numbers of
neutrons.
Isotope Protons Electrons Neutrons Nucleus
Hydrogen–1
(protium) 1 1 0
Hydrogen-2
(deuterium) 1 1 1
Hydrogen-3 1 1 2
(tritium)
Elements
occur in
nature as
mixtures of
isotopes.
Isotopes are
atoms of the
same element
that differ in
the number of
neutrons.
Isobars are the atoms with same mass number
but different atomic number
For example, 14C and 14N.
On the other hand,
Atoms with identical atomic number but
different atomic mass number are known as
Isotopes.
Isotopes have same chemical properties but
different physical properties.
Dual character of electromagnetic radiation
Experimental data regarding Atomic Spectra
Dual character of
electromagnetic radiation
T2
T1
Wave length
At a given temperature, intensity of
radiation emitted increases with decrease of
wavelength, reaches a maximum value at a
given wavelength and then starts decreasing
with further decrease of wavelength.
The above experimental results cannot be
explained satisfactorily on the basis of the
wave theory of light.
Quantized Energy and Photons
Lyman series
Balmer series
Paschen series
Brackett series
Pfund series
Series n1 n2 Region
Lyman 1 2,3….. Ultraviole
t
Balmer 2 3,4……… Visible
Paschen 3 4,5……… Infrared
Brackett 4 5,6…….. Infrared
Pfund 5 6,7……… Infrared
Rutherfords model is in trouble: an
“accelerated charge” should fall into nucleus
electrons in orbits
nucleus
HELIUM ATOM
Shell
proton
N
+ -
+
- N
electron neutron
Bohr suggests that electrons can only exist in
certain orbits
Line spectrum result from the release of
photons as electrons fall back to lower orbit
BOHR’S MODEL
FOR HYDROGEN ATOM
POSTULATES
The electron in the hydrogen atom can
move around the nucleus in a circular path
of fixed radius and energy. These paths are
called orbits, stationary states or allowed
energy states. These orbits are arranged
concentrically around the nucleus.
The energy of an electron in the orbit does
not change with time. However, the electron
will move from a lower stationary state to a
higher stationary state when required amount
of energy is absorbed and energy is emitted
when electron moves from higher stationary
state to lower stationary state. The energy
change does not take place in a continuous
manner.
The frequency of radiation absorbed or
emitted when transition occurs between two
stationary states that differ in energy by ΔE,
is given by :
ν= ΔE/h= (E1 - E2)/h
Where E1 and E2 are the energies of the
lower and higher allowed energy states
respectively.
It is commonly known as Bohr’s frequency
rule.
The angular momentum of an electron in a
given stationary state can be expressed as in
equation
mev r= n.h/2∏ where n=1,2,3…….
Features of Bohr’s Model of atom
The stationary states for electron are
numbered n = 1,2,3.......... These integral
numbers are known as Principal quantum
numbers.
The radii of the stationary states are
expressed as :
rn = n2 a0
where a0 = 52.9 pm.
The energy of stationary state is given by the
expression.
En=-RH.(1/n2)
RH is called Rydberg constant (2.18×10–18 J)
n-Principal quantum number
Explanation of
Line Spectrum of Hydrogen
Energy absorbed or emitted is equal to:
ΔE = Ef – Ei
Ef and Ei are final and initial energy levels.
ΔE = [-RH/(nf)2] -[-RH/(ni)2]
= RH{[1/(ni)2]–[1/(nf)2]}
ν= ΔE/h
= RH{[1/(ni)2]–[1/(nf)2]}/h
ν is the frequency of radiation emitted or absorbed
Limitations of Bohr’s Model
It fails to account for the finer details (doublet, that
is two closely spaced lines) of the hydrogen atom
spectrum observed.
This model is also unable to explain the spectrum
of atoms other than hydrogen.
Bohr’s theory was also unable to explain the
splitting of spectral lines in the presence of
magnetic field (Zeeman effect) or an electric field
(Stark effect).
It could not explain the ability of atoms to form
molecules by chemical bonds.
TOWARDS QUANTUM MECHANICAL
MODEL OF THE ATOM
Two important developments which
contributed significantly in the formulation
of such a model were :
1. Dual behaviour of matter,
2. Heisenberg uncertainty principle.
The Wave Behavior of Matter
• Knowing that light has a particle nature, it seems
reasonable to ask if matter has a wave nature.
• Using Einstein’s and Planck’s equations, de
Broglie showed: h
mv
• The momentum, mv, is a particle property,
whereas is a wave property.
• de Broglie summarized the concepts of waves and
particles, with noticeable effects if the objects are
small.
Energy and Matter
Size of Particle Wave
Matter Property Property
Large –
Mainly Unobservable
macroscopic
Intermediate –
Some Some
electron
Small –
Few Mainly
photon
The Uncertainty Principle
It is impossible to determine simultaneously, the
exact position and exact momentum (or velocity)
of an electron.
Δx. Δp ≥ h/4∏
Δx . Δ(mv ) ≥ h/4∏
Δx is the uncertainty in position
And Δpx ( or Δvx) is
the uncertainty in momentum
Significance of Uncertainty Principle
It rules out existence of definite paths or
trajectories of electrons and other similar
particles. Hence these are replaced by
probability of finding electron
The effect of Heisenberg Uncertainty
Principle is significant only for motion of
microscopic objects and is negligible for
that of macroscopic objects.
Reasons for the Failure of
the Bohr Model
It did not considered the wave character of
electron.
It contradicts Heisenberg uncertainty
principle.
Quantum Mechanical Model
The branch of science that
takes into account the dual
behaviour of matter is
called quantum mechanics.
Quantum mechanics was
developed independently in
1926 by Werner Heisenberg
and Erwin Schrödinger.
Quantum Mechanics and Atomic Orbitals
• Schrödinger proposed an equation that contains both wave and
particle terms.
E is energy &H is a mathematical operator called
Hamiltonian
^
H E
• Solving the equation leads to wave functions.
• The wave function ψ gives the shape of the electronic orbital.
[“Shape” really refers to density of electronic charges.]
• The square of the wave function, gives the probability of finding the
electron (electron density)
Quantum Mechanics and Atomic Orbitals
Solving
Schrodinger’s
Equation gives rise
to ‘Orbitals.’
These orbitals
provide the electron
density distributed
about the nucleus.
Orbitals are
described by
Quantum Mechanics and Atomic Orbitals
Orbitals and Quantum Numbers
• Schrödinger’s equation requires 3 quantum numbers:
1. Principal Quantum Number, n. This is the
same as Bohr’s n. As n becomes larger, the atom
becomes larger and the electron is further from
the nucleus. It determines the size and energy of
the orbital. n = 1 , 2 , 3 , 4 , …. Represents shells
K,L,M,N….
2. Azimuthal Quantum Number, l. This
quantum number depends on the value of n. The
values of l begin at 0 and increase to (n - 1). We
usually use letters for l (s, p, d and f for l = 0, 1,
2, and 3). Usually we refer to the s, p, d and f-
orbitals. It represents shape of the orbital.
n=1, l=0
n=2, l=0,1
n=3, l=0,1,2
n=4, l=0,1,2,3
3. Magnetic Quantum Number, ml. This
quantum number depends on l . The magnetic
quantum number has integral values between -
l and + l . Magnetic quantum numbers give
the 3D orientation of each orbital.
l=0, ml =0
l=1, ml =+1,0,-1
l=2, ml =+2,+1,0,-1,-2
l=3, ml =+3,+2,+1,0,-1,-2,-3
Three quantum numbers are not enough to
explain the line spectra observed in the case of
multi-electron atoms, that is, some of the lines
actually occur in doublets (two lines closely
spaced), triplets (three lines, closely spaced) etc.
This suggests the presence of a few more energy
levels than predicted by the three quantum
numbers.
In 1925, George Uhlenbeck and Samuel
Goudsmit proposed the presence of the fourth
quantum number known as the electron spin
quantum number (ms).
Electron spin quantum number (ms).
Spin angular momentum of the electron can have
two orientations relative to the chosen axis. These
two orientations are distinguished by the spin
quantum numbers ms which can take the values of
+½ or –½. These are called the two spin states of
the electron and are normally represented by two
arrows, ↑ (spin up) and ↓ (spin down). An orbital
cannot hold more than two electrons and these
two electrons should have opposite spins.
Quantum Numbers of Wave functions
Quantum # Symbol Values Description
Principal n 1,2,3,4,… Size & Energy of orbital
Angular l 0,1,2,…(n-1) Shape of orbital
Momentum for each n
Magnetic ml -l…,0,…+ l Relative orientation of
for each l orbitals within same l
Spin ms +1/2 or –1/2 Spin up or Spin down
Angular Momentum Quantum # Name of Orbital
l
0 s (sharp)
1 p (principal)
2 d (diffuse)
3 f (fundamental)
Quantum Mechanics and Atomic Orbitals
Orbitals and Quantum Numbers
Shapes of Atomic Orbitals
On plotting ψ2 (electron density) against r (radius),the
following graph was obtained.
1s 2s
ψ2 ψ2
r r
On both cases the probability of finding
electron decreases as we move away from the
nucleus. But in 2s, there is an increase in the
electron density and then again decreases.
The region where the probability of finding
electron is zero is called nodes. Nodes can be
calculated using the equation, (n-1)
Shapes of Orbitals
Shapes of orbitals are represented by
boundary surface diagrams.
Representations of Orbitals
The s-orbitals
Representations of Orbitals
The p-orbitals
The d-orbitals
Filling of orbitals in atom
Aufbau Principle
The word ‘aufbau’ in German means ‘building up’.
In the ground state of the atoms, the orbitals are
filled in the increasing order of energies.
The principle means that electrons first occupy the
lowest energy orbital available to them and enter
into higher energy orbitals only after the lower
energy orbitals are filled.
Orbitals and Their Energies
Many-Electron Atoms
The order in which the energies of the orbitals
increase and hence the order in which the orbitals
are filled is as follows :
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f,5d, 6p,
7s...
The lower the value of (n + l) for an orbital, the
lower is its energy. If two orbitals have the same
value of (n + l), the orbital with lower value of n
will have the lower energy.
Many-Electron Atoms
Electron Spin and the Pauli Exclusion Principle
Electron Spin and the
Pauli Exclusion Principle