ATOMIC STRUCTURE

All Bold Numbered Problems

1

Chapter 7 Outline
Events leading to Quantum Mechanics
Newton
Planck
Einstein
Bohr
de Broglie
Schrdinger
Heisenberg
Using Quantum Numbers

ATOMIC STRUCTURE
From the ERA of
Newtonian Physics to
Quantum Physics

ELECTROMAGNETIC
ELECTROMAGNETIC
RADIATION
RADIATION

Electromagnetic
Electromagnetic Radiation
Radiation
Most subatomic particles behave as
PARTICLES and obey the physics of
waves.
Define properties of waves
Figure 7.1 and7.2.

Wavelength,
Node
Amplitude
5

Figures 7.1
Electromagnetic Frequency

Electromagnetic
Electromagnetic Radiation
Radiation
wavelength

Visible light

There are
no
Amplitude

LIMITS
to ...

Wavelength ()
Ultraviolet radiation

Node

there are
an
7

Electromagnetic
Electromagnetic Radiation
Radiation
wavelength

Visible light

Amplitud
e
wavelength
Ultaviolet
radiation

Nod
e

Node in a standing
wave
8

Electromagnetic
Electromagnetic Radiation
Radiation

Waves have a frequency

Use the Greek letter nu,
units are cycles per sec

All radiation:

, for frequency, and

= c

where c = velocity of light = 3.00x10 8 m/sec

Long wavelength ----> small frequency
Short wavelength ----> high frequency
9

Electromagnetic
Electromagnetic Radiation
Radiation
Long wavelength -----> small frequency
Short wavelength -----> high frequency

increasing
frequency

increasing
wavelengt
h

See Figure 7.3

10

Figure 7.3

Long wavelength -----> small frequency

Short wavelength -----> high frequency

11

Electromagnetic
Electromagnetic Radiation
Radiation
Red light has = 700. nm.
Calculate the frequency.
1 x 10 -9 m
700 nm
= 7.00 x 10-7 m
1 nm
Freq =

3.00 x 10 8 m/s
7.00 x 10 -7 m

4.29 x 1014 sec -1

Examples

12

Standing
Standing
Waves
Waves

1st vibration

1st vibration =
2nd vibration = 2( )
3rd vibration = 3( )

2nd vibration

See Figure 7.4

13

Newtonian Physics Breakdown

-Quantization of EnergyIt was believed that like wave theory,
energy was also continuous.

Max Planck
(1858-1947)
Solved the
ultraviolet
catastrophe
14

Figure 7.5
Intensity should
Increase with
Decreasing . As you
add more energy,
atoms should vibrate
with a higher energy,
in a continuous
Objects
can gain or
fashion.

lose energy by
absorbing or
emitting radiant
energy in QUANTA.
15

Quantization
Quantization of
of Energy
Energy
Energy of a vibrating system (electromagnetic radiation) is proportional to
frequency.

Ep = h
h = Plancks constant = 6.6262 x 10 -34 Js
We now MUST abandon the idea that
Energy acts as a continuous wave!
16

From Planck on to Einstein

17

Photoelectric
Photoelectric Effect
Effect
A. Einstein (1879-1955)
Experiment demonstrates the particle
nature of light. (Figure 7.6)
Classical theory said that E of ejected
electron should increase with increase
in light intensitynot observed!
No e- observed until light of a certain
minimum E is used &
Number of e- ejected depends on light
intensity.
18

Photoelectric
Photoelectric Effect
Effect
Experimental observations says that light
consists of particles called PHOTONS
having discrete energy.
It takes a high energy particle to bump
into an atom to knock its electron out,
hence the use of a mv2 term.
It would take some minimum energy i.e.
critical energy to knock that electron
away from its atom.

19

Energy
Energy of
of Radiation
Radiation
PROBLEM: Calculate the energy of
1.00 mole of photons of red light.
= 700. nm ( c = )
= 4.29 x 1014 sec-1
Ep = h
= (6.63 x 10-34 Js)(4.29 x 1014 sec-1)
= 2.85 x 10-19 J/photon
Notice Einstein's use of Planck's formula. 20

Energy
Energy of
of Radiation
Radiation
Energy of 1.00 mol of photons of red light.
Ep = h
= (6.63 x 10-34 Js)(4.29 x 1014 sec-1)
= 2.85 x 10-19 J per photon

E per mol =
(2.85 x 10-19 J/ph)(6.02 x 1023 ph/mol)
= 171.6 kJ/mol
This is in the range of energies that can break
bonds.
21

Photoelectric
Photoelectric Effect
Effect
A minimum frequency is required to cause any current
flow. Above that frequency, the current is related to
the intensity of the light used. The ejected electrons
(since we are talking about collisions between photons
and electrons) also have more kinetic energy when
higher frequencies are used.

EK =

1/2 meve2

= Einput - Eminimum

Einstein finds:
Ep = h = 1/2 meve2, evidence that photons have both
wave/particle properties
22

Photoelectric
Photoelectric Effect
Effect
Light is used to eject an electron
from a metal. Calculate the velocity
of the ejected electron if the photon
used to eject the electron has a
wavelength of 2.35 x 10 -7 m and the
minimum frequency required to
eject an electron is 8.45 x 10 14 s-1.
Step by step!!
23

The Final Crack in Classical,

Newtonian Physics
MONUMENTAL Edifice
Planck---Energy is NOT Continuous like
waves
Einstein---Energy comes in packets or is
Quantized and energy also has some
wave and particle behavior
Bohr---Applies Quantized idea to atomic
particles.the H1 Atom to explain..
24

Atomic
Atomic Line
Line Spectra
Spectra and
and
Niels
Niels Bohr
Bohr
Bohrs greatest contribution to
science was BUILDING a
SIMPLE MODEL of the ATOM.

Niels Bohr
(1885-1962)

It was based on an
understanding of the LINE
SPECTRA of excited atoms
and its relationship to
quantized energy.
25

Line
Line Spectra
Spectra
of
of Excited
Excited Atoms
Atoms
Excited atoms emit light of only certain
wavelengths (Planck).
The wavelengths of emitted light depend on the
element.

26

Figure 7.7

27

Figure 7.8

28

Figure 7.9

29

Line Spectra
of Excited Atoms
High E
Short
High

Low E
Long
Low

Visible lines in H atom spectrum are

called the BALMER series.
30

Shells or Levels!!

Why??

31

Figure
7.12
32

Excited Atoms Emit Light

33

Atomic
Atomic Spectra
Spectra and
and Bohr
Bohr
One view of atomic structure in early 20th
century was that an electron (e-) traveled about
the nucleus in an orbit.
Electron
Orbit

1. Any orbit (like a wave-see slide 3) should be

possible and so should any energy.
2. But a charged particle would always be
accelerating from the nucleus (vector velocity is
always changing) and since it is moving in an
electric field would continuously emit energy.
End result should be destruction since the energy
mentioned in the previous step is finite!
34

Atomic
Atomic Spectra
Spectra and
and Bohr
Bohr
Bohr said classical (Newtonian) view is wrong!!!.
Need a new theory now called QUANTUM or
WAVE MECHANICS.
e- can only exist in certain discrete orbits
called stationary states.
e- is restricted to QUANTIZED energy states.

Energy of state, En = - C/n2

where n = quantum no. = 1, 2, 3, 4, ....
this describes the potential energy of an electron
35

Atomic
Atomic Spectra
Spectra and
and Bohr
Bohr
Energy of quantized state, En = - C/n2
Only orbits where n = integral
numbers are permitted.
Radius of allowed orbitals, Rn, Rn=
n2 R0 with Ro = 0.0529 nm
Note the same equations come
from modern wave mechanics
approach.
Results can be used to explain
atomic spectra.
36

Atomic
Atomic Spectra
Spectra and
and Bohr
Bohr
If e-s are in quantized energy
states, then E of states can
have only certain values. This
explain sharp line spectra.
2

n=2

n=1

E = -C ( 1/2
)

E = -C ( 1/1
)

37

Atomic
Atomic
Spectra
Spectra
and
and Bohr
Bohr

E
N
E
R
G
Y

E = -C (1/ 22 )

E = -C

(1/ 1 2 )

n =2

n =1

Calculate E for e- falling from high energy

level (n = 2) to low energy level (n = 1).

E = Efinal - Einitial = - C [ (1/1)2 - (1/2)2 ]

E = - (3/4) C
Note that the process is exothermic!
38

Atomic
Atomic
Spectra
Spectra
and
and Bohr
Bohr

E
N
E
R
G
Y

E = -C (1/ 2 2 )

E = -C

(1/ 1 2 )

n =2

n =1

E = - (3/4)C
C has been found from experiment and is
proportional to RH, the Rydberg constant.
RHhc = C = 1312 kJ/mole.
of emitted light = (3/4)C = 2.47 x 1015 sec-1
and = c/ = 121.6 nm
This is exactly in agreement with experiment!
39

Line
Line Spectra
Spectra
of
of Excited
Excited Atoms
Atoms
E = Efinal - Einitial = - RHhc [ (1/nfinal2) - (1/ninitial2) ]
A photon of light with frequency 8.02 x 1013 s-1
is emitted from a hydrogen atom when it deexcites from the n = 8 level to the n = ? level.
Calculate the final quantum number state of
the electron.
40

Atomic
Atomic Line
Line Spectra
Spectra and
and
Niels
Niels Bohr
Bohr

Niels Bohr
(1885-1962)

Bohrs theory was a great

accomplishment.
Recd Nobel Prize, 1922
Problems with theory
theory only successful for H and
only 1e- systems He+, Li2+.
introduced quantum idea
artificially.
However, Bohrs model does not
explain many e- systems.So, we
go on to QUANTUM or WAVE
MECHANICS
41

Quantum
Quantum or
or Wave
Wave Mechanics
Mechanics
de
de Broglie
Broglie (1924)
(1924) proposed
proposed
that
that all
all moving
moving objects
objects
have
have wave
wave properties.
properties.
For
For light:
light: EE == mc
mc22
L. de Broglie
(1892-1987)

= h
mv

EE == hh == hc
hc //
Therefore,
Therefore, mc
mc == hh //
and
and for
for particles
particles
(mass)(velocity)
(mass)(velocity) == hh //

the
the wave-nature
wave-nature of
of matter.
matter.

Quantum
Quantum or
or Wave
Wave
Mechanics
Mechanics
Baseball (115 g) at 100 mph
= 1.3 x 10-32 cm
e- with velocity =
1.9 x 108 cm/sec
= 0.388 nm
Experimental proof
of wave properties
of electrons
43

Quantum
Quantum or
or Wave
Wave Mechanics
Mechanics
Schrdinger applied
idea of e- behaving as
a wave to the problem
of electrons in atoms.
He developed the
E. Schrdinger
1887-1961

WAVE EQUATION.

44

Quantum
Quantum or
or Wave
Wave Mechanics
Mechanics
Solution of the wave
equation give a set of
mathematical
expressions called

WAVE FUNCTIONS,
E. Schrodinger
1887-1961

Each describes an
allowed energy state of
an e-.
Quantization is
introduced naturally.
45

WAVE FUNCTIONS,
is a function of distance and two angles.
Each corresponds to an ORBITAL the region of
space within which an electron is found.
does NOT describe the exact location of the electron.
2 is proportional to the probability of finding an e - at a
given point.

46

Uncertainty
Uncertainty Principle
Principle

W. Heisenberg
1901-1976

Problem
Problem of
of defining
defining nature
nature
of
of electrons
electrons in
in atoms
atoms
solved
solved by
by W.
W. Heisenberg.
Heisenberg.
Cannot
Cannot simultaneously
simultaneously
define
define the
the position
position and
and
momentum
momentum (=
(= m
mv)
v) of
of an
an
electron.
electron.
We
We define
define ee--energy
energy exactly
exactly
but
but accept
accept limitation
limitation that
that
we
we do
do not
not know
know exact
exact
position.
position.
47

QUANTUM
QUANTUM NUMBERS
NUMBERS
Each orbital is a function of 3 quantum
numbers:

n, l, and ml
Electrons are arranged in shells(levels)
and subshells(sublevels).

n
l
ml

--> shell
--> subshell
--> designates an orbital within a subshell
48

QUANTUM NUMBERS

Symbol

Values

Description

n (major) 1, 2, 3, .. Orbital size

where E = - RHhc(1/n2)

and energy

l (angular) 0, 1, 2, .. n-1
(subshell)

Orbital shape

ml (magnetic)

Orbital

- l..0..+ l

or type

orientation

# of orbitals in subshell = 2 l + 1

49

All 4 Quantum Numbers

Principle quantum number (n)

Azimuthal quantum number (l)
Magnetic quantum number (m)
Spin quantum number (s)

50

Atomic Orbitals the result of

Quantum Mechanics Calculations

51

Shells
Shells and
and Subshells
Subshells
When n = 1, then l = 0 and ml = 0 .
Therefore, if n = 1, there is 1 type of
subshell and that subshell has a
single orbital.
(ml has a single value ---> 1 orbital)
This subshell is labeled s
Each shell has 1 orbital labeled s, and
it is SPHERICAL in shape.
52

1s Orbital

53

2s Orbital

54

3s Orbital

55

56

Atomic Orbitals the result of

Quantum Mechanics Calculations

57

p Orbitals
When
When nn == 2,
2, then
then ll == 00 and
and 11
Therefore,
Therefore, in
in the
the nn == 22 shell
shell
there
there are
are 22 types
types of
of
orbitals
orbitals
22 subshells
subshells
For
For ll == 00 m
ml l == 00
this
this is
is an
an s
s subshell
subshell
For
For ll == 11 m
ml l == -1,
-1, 0,
0, +1
+1
this
this is
is aa p
p subshell
subshell
with
with 3
3 orbitals
orbitals

Typicalporbital

planarnode

When l = 1, there is
a
PLANAR NODE
thru
the nucleus.

See Figure 7.16

58

59

pp Orbitals
Orbitals

A p orbital

The three p
orbitals lie 90o
apart in space
60

2px Orbital

61

2py Orbital

62

2pz Orbital

63

3px Orbital

64

3py Orbital

65

3pz Orbital

66

dd Orbitals
Orbitals
When n = 3, what are the values of l?

l = 0, 1, 2
and so there are 3 subshells in the shell.
For l = 0, ml = 0
---> s subshell with a single orbital
For l = 1, ml = -1, 0, +1
--->

p subshell with 3 orbitals

For l = 2, ml = -2, -1, 0, +1, +2

--->

d subshell with 5 orbitals

67

dd Orbitals
Orbitals

typicaldorbital

s orbitals have no planar

node (l = 0) and so are
spherical.
p orbitals have l = 1, and
have 1 planar node, and
so are dumbbell
shaped.
This means d orbitals,
l = 2) have
2
planar nodes

planarnode

planarnode

See
See Figure
Figure 7.16
7.16

68

3dxy Orbital

69

3dxz Orbital

70

3dyz Orbital

71

3d Orbital
2
z

72

3d

2 2
x -y

Orbital

73

ff Orbitals
Orbitals
When n = 4, l = 0, 1, 2, 3 so there are 4 subshells in
the shell.
For l = 0, ml = 0
---> s subshell with single orbital
For l = 1, ml = -1, 0, +1
---> p subshell with 3 orbitals
For l = 2, ml = -2, -1, 0, +1, +2
---> d subshell with 5 orbitals

For l = 3, ml = -3, -2, -1, 0, +1, +2, +3

---> f subshell with 7 orbitals

74

Orbitals and Quantum Numbers

n

ml

10

1s

20
21
21
21

0
1
0
-1

2s

2p

75

Orbitals and Quantum Numbers

n

30
31
31
31

0
1
0
-1

3
3
3
3
3

ml
3s

3p
2
2
2
2
2

2
1
0
-1
-2

3d

76

Sample
Sample Problems
Problems
No 1. Is it possible to have a d orbital in level 1?
Yes 2. Is it possible to have a 6s subshell?
One 3. How many orbitals are in a 7s sublevel?
9 4. How many orbitals are possible if n = 3?
5. What type of orbital has the quantum
numbers
a) n = 5, l = 2, ml = 1
5d
b) n = 3, l = 2, ml =-1
3d
c) n = 6, l = 3, ml = -3

6f
77

Practice Problems
1. Calculate the wavelength of a photon
having an energy of 2.58 x 10-18 J.
2. In the hydrogen atom, which transition,
3 --> 2 or 2 --> 1, has the longer
wavelength?
3. Calculate the wavelength of an
object (mass = 545 lbs) with a speed of
45 miles/hour.
4. Give all possible sets of quantum
numbers for 4p, 3d, and 5s.
5. How many orbitals are in the
a. the third level?
b. l = 3 sublevel?
78

Practice Problems Answers

1. 7.71 x 10-8

2. 3 --> 2

3. 1.3 x 10-37 m

5. a) 9

4. 4p

b) 7

ml

4
1
1
4
1
0
4
1
-1
Problem 4 continued on next slide.
79

Practice Problems Answers

3d

5s

ml

3
3
3
3
3

2
2
2
2
2

2
1
0
-1
-2

80

Sample
Sample Problem
Problem
1. Calculate the frequency of light having a
wavelength of 1 x 10-7m.

= c
1 x 10-7m . = 3.00 x 108 m/s
= 3 x 1015 /s
81

Sample
Sample Problem
Problem
2. Calculate the wavelength of light having a
frequency of 1.5 x 108 hz.

= c
. x /s = 3.00 x 108 m/s
= 2.0 m
82

Sample
Sample Problem
Problem
3. Calculate the frequency of light having a
wavelength of 1 x 103nm.

= c
1 x 10-6m . = 3.00 x 108 m/s
= 3 x 1014 /s
83

Practice
Practice Problem
Problem
1. Calculate the energy of a photon having a
frequency of 3 x 1015/s.

Ep = h
Ep = 6.63 x 10-34 Js 3 x 1015/s
= 2 x 10-18 J
84

Practice
Practice Problem
Problem
2. Calculate the frequency of light having an
energy of 2.0 x 105 J/mole.

Ep = h
2.0 X 105 J mole
mole

6.02 x 1023 photon

3.3 x 10-19 J = 6.63 x 10-34 Js

= 5.0 x 1014 /s
85

Practice
Practice Problem
Problem
3. Calculate the energy of a photon with a
wavelength of 575 nm.

= c

5.75 x 10-7 m = 3.00 x 108 m/s

= 5.22 x 1014/s

Ep = h
Ep = 6.63 x 10-34 Js 5.22 x 1014/s
= 3.46 x 10-19 J
86

Calculate the energy of the photon:

Photon wavelength = 2.35 x 10 -7 m

= c

2.35 x 10-7 m = 3.00 x 108 m/s

= 1.28 x 1015/s

Ep = h
Ep = 6.63 x 10-34 Js 1.28 x 1015/s
= 8.49 x 10-19 J
87

Calculate the min. energy to eject an electron:

Min. = 8.45 x 10 14 s-1.

Ep = h
Ep = 6.63 x 10-34 Js 8.45 x 1014/s
= 5.60 x 10-19 J

88

Calculate the extra energy of the electron:

8.49 x 10-19 J - 5.60 x 10-19 J = 2.89 x 10-19 J
Calculate the velocity of the electron:

E = 1/2 m v2
2.89 x 10-19 J = (1/2) 9.11 x 10-31 kg v2
= 7.96 x 105 m/s
89

Calculate the energy of the photon:

Ep = h
Ep = 6.63 x 10-34 Js 8.02 x 1013/s
5.32 X 10-20 J 6.02 x 1023 photon
photon

mole

= 3.20 x 104 J = 32.0 kJ

90

Calculate the level number :

Ep = h
E = -C [(1/n)2 - (1/n)2]
-32. kJ = -1312 kJ [(1/n)2 - (1/8)2]
n=5

91