PowerPoint Lecture Presentation

by
J. David Robertson
University of Missouri

Quantum Theory and the

Electronic Structure of Atoms
Chapter 7
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Properties of Waves

Wavelength () is the distance between identical points on

successive waves.
Amplitude is the vertical distance from the midline of a
wave to the peak or trough.
7.1

Properties of Waves

Frequency () is the number of waves that pass through a

particular point in 1 second (Hz = 1 cycle/s).
The speed (u) of the wave = x

7.1

Maxwell (1873), proposed that visible light consists of

electromagnetic waves.
Electromagnetic
radiation is the emission
and transmission of energy
in the form of
electromagnetic waves.

Speed of light (c) in vacuum = 3.00 x 108 m/s

All electromagnetic radiation
x c

7.1

7.1

A photon has a frequency of 6.0 x 104 Hz. Convert

this frequency into wavelength (nm). Does this frequency
fall in the visible region? or Is this AM or FM frequency?

x=c
= c/
= 3.00x108 m/s/6.0x104 Hz
= 5.0 x 103 m
= 5.0 x 1012 nm

Radio wave
7.1

Mystery #1, Black Body Problem:

Frequency dependence of radiation from a heated body
Classical Physics couldnt explain it : UV Catastrophe.
Solved by Planck witth a Quantum Theory (1900)

Energy (light) is emitted or absorbed

in discrete units or a packet (quantum).
Energy of an atom is quantized.
E = nh
h = 6.63 x 10-34 Js
Plancks constant

n: 1,2,3,4,5 etc.
7.1

Whats nature of light?

According to classical physics, it is a wave
because of the following properties.

Reflection
Refraction
Diffraction: a result of interference
However, the wave nature of light couldnt
explain the photoelectric effect.

Mystery #2, Photoelectric Effect

Solved by Einstein in 1905

Electrical Current generated by light:

Presence of the Threshold frequency

KE e-

Absence of Time Lag

Light has both:

1. wave nature
2. particle nature

E = h

Photon is a particle of light

h = KE + BE
KE = h - BE
Alkali metals works the best.

7.2

When copper is bombarded with high-energy

electrons, X rays are emitted. Calculate the energy
(in joules) associated with the photons if the
wavelength of the X rays is 0.154 nm.

E=hx
E = h x c /
E = 6.63 x 10-34 (Js) x 3.00 x 10 8 (m/s) / 0.154 x 10-9 (m)
E = 1.29 x 10 -15 J/photon
= (1.29 x 10 -15 J/photon)(6.022 x 1023photon/mol)
= 7.77x108 J/mol = 7.77x105 kJ/mol = 777 MJ/mol
Cf. Energy

of a UV light with 200 nm:

598kJ/mol
Energy of a red light with 671 nm (Li): 180kJ/mol
Chemical Bond Energy: 500~1,000 kJ/mol

7.2

Why medicines are stored in a brown glass bottles?

Brown glass blocks high energy portion (green and blue) of

the visible light by absorbing G & B. It also absorb red
portion substantially to impart brown color. Many
chemicals can be destroyed by EMW with higher energy
(Blue ,Violet, UV and others).

Brown (Dark Red) light has much less energy

(<200kJ/mol), thus cannot harm many substances.
Normally 200 kJ/mol or more of energy is needed to break
many chemical bonds.

Red
Lower

Green

Blue
Higher Energy

Mystery #3: Line Emission Spectrum of H Atoms

HOW are they generated?

(396)

410

434

496

.
Johann Balmer (1825-1989) solved the jigsaw puzzle

656

7.3

7.3

The Jigsaw puzzle of the H emission spectra was solved

by Balmer (1885) without knowing its implacations

1/ = 1.097x107 (1/22-1/n2) m-1

= 0.01097 (0.25-1/n2) nm-1
where n = 3,
4,
5,
6,

= 656 nm
= 486
= 434
= 410

Bohrs Model of
the Atom (1913)
1. e- can only have specific
(quantized) energy
values
2. light is emitted as emoves from one energy
level to a lower energy
level

En = -RH (

1
n2

n (principal quantum number) = 1,2,3,

RH (Rydberg constant) = 2.18 x 10-18J
7.3

E = h

E = h

7.3

ni = 3

ni = 3

ni = 2
nf = 2

Ephoton = E = Ef - Ei
1
Ef = -RH ( 2
nf
1
Ei = -RH ( 2
ni
1
E = RH( 2
ni

)
)
1
n2f

nnf f==11
7.3

Calculate the wavelength (in nm) of a photon

emitted by a hydrogen atom when its electron
drops from the n = 5 state to the n = 3 state.
Ephoton = E = RH(

1
n2i

1
n2f

Ephoton = 2.18 x 10-18 J x (1/25 - 1/9)

Ephoton = E = -1.55 x 10-19 J
Ephoton = h x c /
= h x c / Ephoton
= 6.63 x 10-34 (Js) x 3.00 x 108 (m/s)/1.55 x 10-19J
= 1280 nm

Is this IR or UV?
7.3

The Dual Nature of Matter:

Wave-Particle Duality: Wavicle

Einstein:
(1905)

Light wave is Light Particle

(Photon)
E = h = hc/
De Broglie: Electron (Particle) is Wave
(1923)
= h/mu

Why is e- energy quantized?

De Broglie (1924) reasoned

that e- is both particle and
wave.
2r = n

= h/mu

u = velocity of em = mass of e7.4

What is the de Broglie wavelength (in nm)

associated with a 2.5 g Ping-Pong ball
traveling at 15.6 m/s?
= h/mu
h in Js m in kg
= 6.63 x 10-34 / (2.5 x 10-3 x 15.6)

u in (m/s)

= 1.7 x 10-32 m = 1.7 x 10-23 nm

What is the de Broglie wavelength (in nm)

associated with an electron moving at a
speed of 2x108 m/s?
= 6.63 x 10-34 / (9.11x10-35 x 2x108) = 0.004 nm
7.4

Chemistry in Action: Electron Microscopy

e = 0.004 nm

STM image of iron atoms

on copper surface

7.6

Chemistry in Action: Element from the Sun

In 1868, Pierre Janssen detected a new dark line in the solar
emission spectrum that did not match known emission lines
Mystery element was named Helium
In 1895, William Ramsey discovered helium in a mineral of
uranium (from alpha decay).
H:

He: 668

656

486

588

502

434 410

447

Chemistry in Action: Laser The Splendid Light

Laser light is (1) intense, (2) monoenergetic, and (3) coherent

Schrodinger Wave Equation

In 1926 Schrodinger wrote an equation that
described both the particle and wave nature of the e Wave function () describes:
1. energy of e- with a given
2. probability of finding e- in a volume of space
Schrodingers equation can only be solved exactly
for the hydrogen atom. Must approximate its
solution for multi-electron systems.

7.5

Schrodinger Wave Equation

fn(n, l, ml, ms)
principal quantum number n
n = 1, 2, 3, 4, .
distance of e- from the nucleus

n=1

n=2

n=3

7.6

Where 90% of the

e- density is found
for the 1s orbital

e- density (1s orbital) falls off rapidly

as distance from nucleus increases

7.6

Schrodinger Wave Equation

= fn(n, l, ml, ms)
angular momentum quantum number l
for a given value of n, l = 0, 1, 2, 3, n-1

n = 1, l = 0
n = 2, l = 0 or 1
n = 3, l = 0, 1, or 2

l=0
l=1
l=2
l=3

s orbital
p orbital
d orbital
f orbital

Shape of the volume of space that the e - occupies

7.6

l = 0 (s orbitals)

l = 1 (p orbitals)

7.6

l = 2 (d orbitals)

7.6

Schrodinger Wave Equation

= fn(n, l, ml, ms)
magnetic quantum number ml
for a given value of l
ml = -l, ., 0, . +l
if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2
orientation of the orbital in space
7.6

ml = -1

ml = -2

ml = 0

ml = -1

ml = 0

ml = 1

ml = 1

ml = 2

7.6

Schrodinger Wave Equation

= fn(n, l, ml, ms)
spin quantum number ms
ms = + or -

ms = +

ms = -

7.6

Schrodinger Wave Equation

= fn(n, l, ml, ms)
Existence (and energy) of electron in atom is described
by its unique wave function .
Pauli exclusion principle - no two electrons in an atom
can have the same four quantum numbers.

Each seat is uniquely identified (E, R12, S8)

Each seat can hold only one individual at a
time
7.6

7.6

Schrodinger Wave Equation

= fn(n, l, ml, ms)
Shell electrons with the same value of n
Subshell electrons with the same values of n and l
Orbital electrons with the same values of n, l, and ml
How many electrons can an orbital hold?
If n, l, and ml are fixed, then ms = or -

= (n, l, ml, ) or= (n, l, ml, -)

An orbital can hold 2 electrons

7.6

How many 2p orbitals are there in an atom?

n=2
2p

If l = 1, then ml = -1, 0, or +1
3 orbitals

l=1

How many electrons can be placed in the 3d

subshell?
n=3
3d
l=2

If l = 2, then ml = -2, -1, 0, +1, or +2

5 orbitals which can hold a total of 10 e7.6

Energy of orbitals in a single electron atom

Energy only depends on principal quantum number n
l=
0
1
2
3

n=3
n=2

En = -RH (

1
n2

n=1
7.7

Energy of orbitals in a multi-electron atom

Energy depends on n and l

n=3 l = 2
n=3 l = 0
n=2 l = 0

n=3 l = 1
n=2 l = 1

n=1 l = 0
7.7

Fill up electrons in lowest energy orbitals (Aufbau principle)

??
Be
Li
B5
C
3
64electrons
electrons
2 22 2 12 1
BBe
Li1s1s
1s
2s2s
2s
2p
H
He12electron
electrons
He
H 1s
1s12
7.7

The most stable arrangement of electrons

in subshells is the one with the greatest
number of parallel spins (Hunds rule).

Ne97
C
N
O
F
6810
electrons
electrons
electrons
2 222 5
Ne
C
N
O
F 1s
1s222s
2s2p
2p3246

7.7

Order of orbitals (filling) in multi-electron atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
7.7

Electron configuration is how the electrons are

distributed among the various atomic orbitals in an
atom.
number of electrons
in the orbital or subshell

1s1
principal quantum
number n

angular momentum
quantum number l

Orbital diagram
H
1s1
7.8

What is the electron configuration of Mg?

Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s2

2 + 2 + 6 + 2 = 12 electrons

Abbreviated as [Ne]3s2

[Ne] 1s22s22p6

What are the possible quantum numbers for the

last (outermost) electron in Cl?
Cl 17 electrons
1s22s22p63s23p5

1s < 2s < 2p < 3s < 3p < 4s

2 + 2 + 6 + 2 + 5 = 17 electrons

Last electron added to 3p orbital

n=3

l=1

ml = -1, 0, or +1

ms = or -

7.8

Outermost subshell being filled with electrons

7.8

7.8

Paramagnetic

Diamagnetic

unpaired electrons

all electrons paired

2p

O, S

2p

Ne, Ar

7.8