Slide 1 of 58

Chapter One
Atomic Structure
Slide 2 of 58
The abundances of the elements in the
universe
Slide 3 of 58
Subatomic particle of relevance to chemistry
1 0 0
Electromagnetic
radiation from
nucleus
photo
-1 0 e
-
ejected from
nucleus
particle
0 +2 4
2
4
He
2+
nucleus particle
+1 0 5.486 x 10
-4
e
+
Positron
0 0 c. 0 Neutrino
0 1 1.0087 n Neutron
+1 1 1.0073 p Proton
-1 0 5.486 x 10
-4
e
-
Electron
Spin Charge/
e
#
Mass
number
Mass/u* Symbol Particle
*Masses are expressed in atomic mass units, u, with 1 u = 1.6605 x 10
-27
kg
#
Elementary charge e = 1.602 x 10
-19
C.
Slide 4 of 58
Nuclear Binding Energy
for Helium
E
bind
= (m)C
2
Slide 5 of 58
Average Binding Energies
Slide 6 of 58
Rutherfords Alpha Scattering
Experiment
Slide 7 of 58
Rutherfords Model
Ernest Rutherford discovered the positive charge of
an atom is concentrated in the center of an atom,
the nucleus
An atom, can be visualized as a giant indoor
football stadium
The nucleus can be represented by a pea in the
center of the stadium,
The electrons are a few bees buzzing throughout.
The roof of the stadium prevents the bees from
leaving.
Slide 8 of 58
Continuous
Spectra
Line
Spectra
Slide 9 of 58
Emission Spectrum of Hydrogen
in Visible Light Region
Slide 10 of 58
Line Spectra of Some
Elements
Slide 11 of 58
Plancks Constant
Plancks quantum hypothesis states that energy can be
absorbed or emitted only as a quantum or as whole
multiples of a quantum, thereby making variations
discontinuous, changes can only occur in discrete
amounts.
The smallest amount of energy, a quantum, is given by:
E = hv
as Plancks constant, h =6.626 X 10
-34
J s.
Slide 12 of 58
The Photoelectric Effect
Albert Einstein considered electromagnetic energy
to be bundled in to little packets called photons.
Energy of photon = E = hv
Photons of light hit surface electrons and transfer
their energy hv = B.E. + K.E.
The energized electrons overcome their attraction
and escape from the surface
hv
e
-
(K.E.)
Slide 13 of 58
Bohrs Hydrogen Atom
v
e-
r
Z
Orbit
Postulations
Rutherfords nuclei model
The energy of an electron in a H atom is quantized
Planck & Einsteins photon theory
E = hv
Electron travels in a circle
Classical electromagnetic theory is not applied
Slide 14 of 58
(1) Classical physics
centripetal force = Coulombic attraction
mv
2
/r = Ze
2
/r
2
E = - ( 2
2
mZ
2
e
4
)/(n
2
h
2
)
when n =1, E
(1)
= - (2
2
mZ
2
e
4
)/( h
2
)
E = E
(1)
/n
2
r = (n
2
h
2
)/ (4
2
mZe
2
)
(2) Total energy
E = 1/2 mv
2
- Ze
2
/r
(3) Quantizing the angular momentum
mvr = n(h/2 )
Quantum number
Slide 15 of 58
Bohrs Hydrogen Atom
Niels Bohr found that the electron energy (E
n
) was
quantized, that is, that it can have only certain specified
values.
Each specified energy value is called an energy level of
the atom
E
n
= - B/n
2
n is an integer, and B is a constant which equals
2.179 x 10
-18
J
The energy is zero when the electron is located
infinitely far from nucleus
The negative sign represents the forces of attraction
Slide 16 of 58
The Bohr Model
Slide 17 of 58
Bohr Explains Line Spectra
Bohrs equation is most useful in determining the
energy change (E
level
) that accompanies the leap of
an electron from one energy level to another
For the final and initial levels:
E
f
= -B / n
f
2
E
i
= -B / n
i
2
The energy difference between n
f
and n
i
is:
E
level
= E
f
- E
i
= ( -B / n
f
2
) (-B / n
i
2
)
= B(1/n
i
2
1/n
f
2
)
Slide 18 of 58
Energy Levels and Spectral Lines for
Hydrogen
Visible
UV
IR
Slide 19 of 58
Ground States and Excited States
When an atom has its electrons in their lowest possible
energy levels, it is in its ground state
When an electron has been promoted to a higher level, it
is in an excited state
Electrons are promoted through an electric discharge,
heat, or some other source of energy
An atom in an excited state eventually emits photons
as the electron drops back down to the ground state
Slide 20 of 58
Problems of
Bohrs Model of Atom
The energy levels of Bohrs H atom cannot
be applied to other atoms.
The orbit of electrons cannot be defined.
Slide 21 of 58
The Uncertainty Principle
Werner Heisenbergs uncertainty principle states
that we cant simultaneously know exactly where a
tiny particle like an electron is and exactly how it is
moving
(P
x
) (x) = h/4 = P
x
= mv
x
2
h
h
2
h
The act of measuring the particle actually interferes
with the particle
In light of the uncertainty principle, Bohrs model of
the hydrogen atom fails, in part, because it tells more
than we can know with certainty.
Slide 22 of 58
Uncertainty Principle Illustrated
Slide 23 of 58
De Broglies Equation
Louis de Broglie speculated that matter can behave
as both particles and waves, just like light
He proposed that a particle move with a mass m
moving at a speed c will have a wave nature
consistent with a wavelength given by the equation:
p = mc
E = mc
2
= pc = h
p = h /c = h/
De Broglies prediction of matter waves led to the
development of the electron microscope
= h/p= h/mc
Slide 24 of 58
What is the speed of an electron to have a wavelength of
X-ray?
Wavelength of X-ray ~ 0.1 nm = 1 x 10
-10
m
Mass of electron = 9.11 x 10
-31
kg
Planck constant h = 6.626 x 10
-34
Js (kg m
2
/s)
<Answer>
= h/p= h/mv
v =h/m = (6.626 x10
-34
)/[(9.11 x10
-31
)(1 x 10
-10
)]
= 7 x10
6
m/s
Slide 25 of 58
How to achieve the speed of an electron of 7 x10
6
m/s?
V
<Answer>
E= eV= mv
2
V = mv
2
/e= (9.11 x10
-31
)(7 x10
6
)
2
/(1.6022 x 10
-19
)
V = 140 V
(1 eV = 1.6022 x 10
-19
J)
Slide 26 of 58
Electron diffraction
The experimental confirmation of de Broglies wave
hypothesis was first made in 1927 by Davisson and
Germer of the Bell Laboratories who investigated the
scattering of electrons from various surfaces.
Slide 27 of 58
Wave Functions
Quantum mechanics, or wave mechanics, is
the treatment of atomic structure through the
wavelike properties of the electron
Wave mechanics provides a probability of
where an electron will be in certain regions of
an atom
Slide 28 of 58
Erwin Schrdinger developed a wave equation to
describe the hydrogen atom
An acceptable solution to Schrdingers wave
equation is called a wave function
A wave function () is characterized by an energy
state of the atom
1 ) , , (
2

+

d z y x
2
) , , ( z y x : the probability of finding an electron
at (x, y, z) position in an atom
The probability of finding
an electron in the universe
is equal to 1.
Slide 29 of 58
x
y
Traveling wave
y(x, t) = y
0
sin(kxt)
y: amplitude of the wave
If y is a function of x only,
then, y(x) = y
0
sinkx
Standing wave
y(x) = y
0
sinkx
Boundary condition:
y = 0, when x = 0
y = 0, when x = L
L
L
x
0
n=1
n=2
n=3
kL = n, k = n/L
n = integers (quantum number)
y(x) = y
0
sin[(n/L) x]
Slide 30 of 58
Standing Waves
&
Quantum Number
Slide 31 of 58
Wave Mechanics
: amplitude of the wave
The probability that a particle will be detected is
proportional to .
E

( ) [ ] 0
8
2
2
2
2
+

x U E
h
m
dx
d
2

Schrdinger equation
one-dimensional
Hamiltonian operator
( )

E x U
dx
d
m
h
+
2
2
2
2
8
( )

E x U
dx
d
m
h

1
]
1

+
2
2
2
2
8
( ) x U
dx
d
m
h
+
2
2
2
2
8

Operator for K.E.

P.E.
P.E.
Slide 32 of 58
( ) [ ] 0 , ,
8
2
2
2
2
2
2
2
2
+

z y x U E
h
m
z y x
three-dimensional Schrdinger equation
( ) z y x U
z y x m
h
, ,
8

2
2
2
2
2
2
2
2
+

,
_

Slide 33 of 58
One-dimensional Schrdinger equation
Particle in a Box
( ) [ ] 0
8
2
2
2
2
+

x U E
h
m
dx
d
2

( ) [ ] 0
8
2
2
2
2
+

x U E
h
m
dx
d
The probability that the
particle will be detected is
proportional to
In the box, 0 < x < L and U = 0

E
dx
d
m

2
2 2
2
h
( ) x U
dx
d
m
h
+
2
2
2
2
8

2
h
h
2
2 2
2
2
2
2
2 8

dx
d
m dx
d
m
h h

[ ] [ ] ) sin( ) sin(
2
2
2 2
kx A E kx A
dx
d
m

h
Let and A, k are constants
) sin( kx A
Slide 34 of 58
[ ] [ ] ) sin( ) sin(
2
2
2 2
kx A E kx A
dx
d
m

h
[ ] [ ] ) sin( ) sin(
2
2
2
kx A k kx A
dx
d

Since
[ ] [ ] ) sin( ) sin(
2
2
2
kx A E kx A k
m

h
m
k
E
2
2 2
h

Boundary conditions for the particle in the box:

1. The particle cannot be outside the box.
2. In a given state, the total probability of finding
the particle in the box must be 1.
3. The wave function must be continuous.
0 ) ( and 0 ) 0 ( L
1 ) (
0
2

dx x
L

Slide 35 of 58
0 ) ( and 0 ) 0 ( condition Boundary L
) sin( ) ( kx A x
x
L
n
A x
n
L
n
k n kL
kL A L

sin ) (
intergers is where , or ,
0 sin ) (

1 ) ( condition Boundary
0
2

dx x
L

2
0
2
0
2 2
0
2
1
) sin(
1 ) sin( ) (
A
dx x
L
n
dx x
L
n
A dx x
L
L L

Slide 36 of 58
L
A
A
L
dx x
L
n
L
2
1
2
) sin(
2
0
2

x
L
n
L
x

sin
2
) (
2
2
2
2
2 2 2
8 2 2

,
_

,
_

L
n
m
h
L
n
m m
k
E

h h
2
2 2
8mL
h n
E

Slide 37 of 58
(normalization)
(x,y,z) is a single valued function w.r.t.
the coordinates
(x,y,z) is a continuous function
(x,y,z) is a finite function
1 ) , , (
2

+

d z y x
Boundary condition for solving in
Schrdinger eq. for an electron in an atom:
Slide 38 of 58
For H atom
r
e
r
Ze
U
2 2

( )
( ) ( ) ( )
( ) ( )


,
, , ) , , (

r R
r R
r z y x
Z= 1
e-
r
x
z
y

To solve the equation more easily,

Cartesian coordinates x, y, z are
transformed to polar coordinates r, , .
Slide 39 of 58
Wavefunctions of Hydrogen Atom
Slide 40 of 58
Slide 41 of 58
Quantum Numbers and
Atomic Orbitals
The wave functions for the hydrogen atom contain three
parameters that must have specific integral values called
quantum numbers.
A wave function with a given set of these three quantum
numbers is called an atomic orbital.
These orbitals allow us to visualize the region in which
there is a probability of find an electron.
Slide 42 of 58
Quantum Numbers
The principal quantum number (n)
Can only be a positive integer
The size of an orbital and its electron energy
depend on the n number
Orbitals with the same value of n are said to be in
the same principle shell
Value of n 1 2 3 4 5
Shell K L M N O
n = 1, 2, 3
When values are given to quantum numbers, a specific
atomic orbital is defined
Slide 43 of 58
Quantum Numbers (continued)
The orbital angular momentum quantum number (l)
Can have positive integral values
0 l n-1
Determines the shape of the orbital
All orbitals having the same value of n and the same
value of l are said to be in the same subshell
Orbitals and subshells are also designated by a letter:
Value of l 0 1 2 3
Orbital or subshell s p d f
Slide 44 of 58
Quantum Numbers (continued)
The magnetic quantum number (m
l
):
Can be any integer from -l to +l
-l m
l
l
Determines the orientation in space of the orbitals of
any given type in a subshell
The number of possible value for m
l
= 2l + 1, and
this determines the number of orbitals in a subshell
Slide 45 of 58
The relationship between quantum
numbers
0 l n-1
For example: n= 1, l= 0
n= 2, l= 1, 0
n= 3, l= 2, 1, 0
-l m
l
l
For example: l= 1, m
l
= -1,0,1
l= 2, m
l
= -2,-1,0,1,2
1s- orbital
2p, 2s- orbitals
3d, 3p, 3s- orbitals
p
x
, p
y
, p
z
- orbitals
d
xy
, d
yz
, d
zx
, d
z
2, d
x
2
-y
2
orbitals
Slide 46 of 58
Slide 47 of 58
Quantum Numbers Summary
Slide 48 of 58
The 1s Orbital
The 1s orbital has spherical symmetry.
The electrons are more concentrated near the center

0, 0
(,) = 1/2
1/2
Slide 49 of 58
(+)
(-)
0
node
r
0
0
The 2s Orbital

0,0
(,) = 1/2
1/2
Slide 50 of 58
The 2s Orbital
The 2s orbital has two regions of high electron
probability, both being spherical
The region near the nucleus is separated from the outer
region by a spherical node- a spherical shell in which
the electron probability is zero
node
Slide 51 of 58
Slide 52 of 58
The Three p Orbitals
Slide 53 of 58
The Five d Orbital Shapes
Slide 54 of 58
The Seven f Orbital Shapes
Slide 55 of 58
Electron Spin the 4
th
Quantum
Number
The electron spin quantum number (m
s
) explains
some of the finer features of atomic emission spectra
The number can have two values: +1/2 and 1/2
( m
s
= , - )
The spin refers to a magnetic field induced by the
moving electric charge of the electron as it spins
The magnetic fields of two electrons with opposite
spins cancel one another; there is no net magnetic
field for the pair.
Slide 56 of 58
The Stern-Gerlach Experiment
Slide 57 of 58
Hydrogen atom and Schrdinger
equation
energy is quantized (n)
magnitude of angular momentum is
quantized (l)
the orientation of angular momentum
is quantized (m
l
)
Electron has spin (m
s
)
Slide 58 of 58
hydrogen atom
2 2
4 2
2 h n
me Z
E