MATTER AS A WAVE & THE

STRUCTURE OF AN ATOM
Instructor: Dr. Mehr Nigar
Photon Momentum

If light is a stream of particles, then each

of these particles must have a momentum
(p).
p = hf/c
since c = f
p = h/
Beginnings of a New Mechanics!

Louis de Broglie (1892-1987)

p = h/

 = h/p

since p = mv
 = h/mv
Theorized in his PhD thesis (1929) that if light can
behave as a particle and have a momentum, matter
can also have a wavelength related to its momentum!

De Broglie “lifted the corner of a great veil.”- Albert Einstein

Wavelength of Shoaib’s fast ball?

velocity = 100 mph (44.7 m/s)

mass = 162g = 0.162kg
 = h/mv
• 6.626 x 10-34kgm2s-2s / (0.162 kg) (44.7 m/s)

 = 9.2 x 10-35 m

Undetectable!
 Which bowler’s fastball has the longest
wavelength?

100 mph (pak vs New Zealand (27/04/02)

44.7m/s

97.8 mph (Australia vs. S. Africa 08/03/02)

43.7 m/s

http://stats.cricinfo.com/ci/content/records

Ashish Nehra
 = 1.04 x 10-34 m

95.9 mph S Africa vs. India, 03/11/01 87.6 mph India vs. West Indies, 21/04/02
42.9 m/s 39.2 m/s
Wavelength of an electron:

v = 44.7 m/s

e- v = 2.998 x 108 m/s / 1000 = 299,800 m/s

 = h / mv = 6.626 x 10-34 kgm2s-2s / (9 x 10-31kg) (299,800 m/s)

2.46 x 10-9 m = 24.6 Å

Detectable!
 Wave Nature of Electron:
 1925 Davisson and Germer were able to observe electron diffraction
from a Ni crystal.
 G.P Thomson showed that electrons that passed through a very thin
gold foil produced a diffraction pattern.

ELECTRONS have both wave-like and particle like properties.

G.P. Thomson was the son of J.J. Thomson. Both received Noble prizes, J.J. for showing that the electron
is a particle and G.P. for showing that it is a wave!
Matter as wave!

Schrodinger Wave Equation:

Describing electrons by their wave properties.

= Wave Function (a way of representing electron)

E = Binding Energy (of the electron to the nucleus)
H = Hamiltonian operator
Shrodinger Equation:
e-
e-

r
+

Wavefunction for electron

Hamiltonian Binding
Operator Energy
Solving the Schrodinger Equation

Finding or wavefunctions or orbitals

Finding E, binding energy of electron to nucleus

Solving for Hydrogen Atom

m = me = mass of an electron 0 = permittivity constant

e = charge on the electron h = Planck’s constant

me4 = RH = Rydberg’s Constant = 2.18 x 10-18 J

80h2
Now the binding energy En = -RH/n2 n = 1,2,3……..

n = principal quantum number

Electron as a Particle in a box!

http://en.wikipedia.org/wiki/Particle_in_a_box
Quantization of Energies
0 n= Free electron
H+ + e-

-0.061 x 10-18 J
-0.087 x 10-18 J

-0.146 x 10-18 J -RH

42

-0.242 x 10-18 -RH

J 32

-RH
-0.545 x 10-18 J
22

-2.180 x 10-18 J ground state

Significance of Binding Energies
En = -IE of an atom in the nth state

i.e. the amount of energy required to ionize an H atom

The IE for an H atom in the ground state is 2.18 x 10-18 J

first excited state

The IE for an H atom in the first excited state is 5.45 x 10-19 J

What is the IE of a H atom in the 2nd excited state?
0
En
1. -0.09 x 10-18 J
- 0.06 x 10-18 J n=6
2. 0.09 x 10-18 J
- 0.09 x 10-18 J n=5
3. -0.14 x 10-18 J
- 0.14 x 10-18 J n=4
4. 0.14 x 10-18 J
5. -0.24 x 10-18 J - 0.24 x 10-18 J n=3
6. 0.24 x 10-18 J
7. -0.54 x 10-18 J
- 0.54 x 10-18 J n=2
8. 0.54 x 10-18 J

- 2.18 x 10-18 J n=1

Energies of single electron atoms:

 En = - Z2RH Correctly predicts the energy levels for any one electron atom!
n2

He+ 1 electron atom Z=2

Li2+ 1 electron atom Z=3

K18+ 1 electron atom Z = 19

U(r) = -(Ze)e / 4π0r

Hydrogen Atom Emission Spectrum

http://www.chemguide.co.uk/atoms/properties/hspectrum.html
Continuous & Quantized Energy
Levels
“Quantized” spectrum
“Continuous” spectrum

DE
DE

Any DE is Only certain

possible DE are
allowed
Emission spectrum of H Atom

Light Bulb

Continuous; NOT quantized

Hydrogen Lamp

Quantized, not continuous

Relaxation of an excited H atom:
 A photon is emitted with the exact energy of the energy difference
between the initial and final states.

ΔE = Ei - Ef

ΔE = En=6 – En=2
Calculating the Frequency of a Photon:

ΔE = Ei - Ef

f = ΔE = Ei – Ef
h h
ΔE = hf
Relationship between E, f and 

Large ΔE
f high
 short

Small ΔE
f low
 long
J.J. Balmer (1885)

f = 3.29 x 1015 s-1 (1/4 – 1/n2)

where n = 3,4,5,……
http://hyperphysics.phy-astr.gsu.edu/hbase/hyde.html
Interpreting Emission Spectra:

f = Ei – Ef
h

6 5 4 3
Calculating the frequency of Emitted
Photons:

f = Ei – Ef En = -RH
h n2

f=1 -RH - -RH

h ni2 nf2

Image taken from Chemical Principles

f= RH 1 – 1
h nf2 ni2
Balmer Series:

RH 1 - 1
f=
h 4 ni2

BALMER SERIES

RH ℜ = 3.29 x 1015 s-1

h

nf = 2
Fitting Constant used by Balmer
Structure of a Hydrogen Atom

http://www.physics-edu.org/line_spectrum_of_hydrogen_atom.htm
What is the IE of a hydrogen atom in the 4th excited state?
0
En
1. -0.06 x 10-18J
2. 0.06 x 10-18 J - 0.06 x 10-18 J n=6
3. -0.09 x 10-18 J - 0.09 x 10-18 J n=5
4. 0.09 x 10-18 J - 0.14 x 10-18 J n=4
5. -0.14 x 10-18 J
- 0.24 x 10-18 J n=3
6. 0.14 x 10-18 J
7. -0.24 x 10-18 J
8. 0.24 x 10-18 J - 0.54 x 10-18 J n=2
9. -0.54 x 10-18 J

- 2.18 x 10-18 J n=1

H Atom Emission Series

Excited States
IR

Paschen Series nf = 3

Balmer Series nf = 2

UV Lyman Series nf = 1

Ground State
Select the most accurate statement about
photon absorption and emission

-e
1. absorption: ni > nf (energy gained by e-)
emission: nf > ni (energy lost by e-)
2. absorption: nf > ni (energy gained by e-)
emission: ni > nf (energy lost by e-)
3. absorption: ni > nf (energy lost by e-)
emission: nf > ni (energy gained by e-)
4. absorption: nf > ni (energy lost by e-
-e emission: ni > nf (energy gained by e-)
Photon Absorption These terms should always be POSITIVE

RH 1 - 1
f= ni2 nf2
h for nf > ni

ΔE high
f high
λ short

absorbed photon

ΔE small
f low
absorbed photon λ long
Sample Problem:
Calculate the wavelength of radiation emitted by a Hydrogen atom when an
electron makes a transition from n = 3 to n = 2 energy level.

f= RH 1 – 1 f= RH 1 – 1
h nf2 ni2 h 22 32 λ = 657 nm

f= RH 5 5 e-
f =ℜ
h 36 36 En = 3

λ = c/f

36c 36 (2.998 x 108 m s-1)

λ= λ=
5ℜ 5 (3.29 x 1015 s-1)

En = 2
λ = 6.57 x 10-7 m λ = 657 nm
Frequency and Energy Calculations for
1 Electron Atoms

Z 2R
H
1 - 1
f= Z 2R 1 - 1
h nf2 ni2 f= H
h ni2 nf2

ni > nf in emission nf > ni in absorption

e-

e-
Solving for Hydrogen Atom

m = me = mass of an electron 0 = permittivity constant

e = charge on the electron h = Planck’s constant

me4 = RH = Rydberg’s Constant = 2.18 x 10-18 J

80h2
Now the binding energy En = -RH/n2 n = 1,2,3……..

n = principal quantum number

Shrodinger Equation and Quantum
Numbers:

Time independent stationary-wave function

n = principal quantum number n = 1, 2, 3,……………..∞

l = angular momentum quantum number l = 0, 1, 2, 3………....(n-1)

ml = magnetic quantum number ml = -l,…..0…..l

A total of three quantum numbers are needed to completely describe a wave

function in 3-D.
Example:
What will be the values of l and ml when n = 3

l=0 ml = 0

l=1 ml = -1, 0, 1

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

Complete Description of a Ground State
Wavefunction ψ
A total of three quantum numbers appear
from the solution of

n = principal quantum number

l = angular momentum quantum number

ml = magnetic quantum number

nlm(r,θ,Φ)
What will a ground state wave-
function be called??
 Correlation of Wavefunctions to Orbitals

Using the terminology of chemists:

100(r,,) is instead called the 1s orbital.
n designates the shell (1, 2, 3, 4,…..)
l designates the sub-shell (s, p, d, f….)
ml completes the description of the orbital
l = 0 (s orbital) l = 1 (p orbital)

l = 2 (d orbital) l = 3 (f orbital)

When l =1 and ml = 0 then orbital is pz When l=1 and ml= ±1 then orbital is px or py
Hydrogen Atom Wavefunctions

n=1 100 100 1s -RH / 12 -2.18 x 10-19J

l =0
m=0
n=2
200 200 2s -RH / 22 -5.45 x 10-19J
l =0
m=0
n=2 2px (or 2py) -RH / 22
211 211 - 5.45 x 10-19J
l =1
m = +1
n=2
210 210 2pz -RH / 22 - 5.45 x 10-19J
l =1
m=0
n=2
l =1 21-1 21-1 2py (or 2px) -RH / 22 - 5.45 x 10-19J
m = -1
What is the corresponding orbital for a
4,1,0 state?
1. 1s
2. 2s
3. 4s
4. 5s
5. 4px
6. 4py
7. 4pz
8. 4dz
Arrangement of Shells/Subshells/Orbitals and
Corresponding Quantum Numbers

En = -RH
n2

For a H-atom, orbitals with same value

of n have equal energy.

For any shell n there are n2 degenerate orbitals.

Energy Levels For a Hydrogen Atom:

3s 3px 3pz 3py 3dxy 3dyz 3dz2 3dxz 3dx2-y2

2s 2px 2pz 2py

1s
Concept Check!
 How many orbitals in a single atom can have the
following two quantum numbers: n = 4, ml = -2
1. one
2. two
3. three
4. four
5. five
6. six
7. seven
8. eight
9. zero
Degeneracy of states

States having the same energy are called

degenerate.
For every value of n there are n2
degenerate states.
Physical Interpretation of Ψ

 Quantum world is very different from the macroscopic world that we are
used to seeing.
 Therefore unfortunately a physical interpretation of Ψ does not exist.
 However a physical interpretation for Ψ2 does exist!

| nlm(r,,)|2 = Probability Density

Probability / Volume

Max Born Figure from MIT Open CourseWare

Electron clouds
 Although we cannot know how the electron travels around
the nucleus we can know where it spends the majority of its
time (thus, we can know position but not trajectory).
 The “probability” of finding an electron around a nucleus
can be calculated.
 Relative probability is indicated by a series of dots,
indicating the “electron cloud”.

• 90% electron probability or cloud for 1s

orbital (notice higher probability toward
the centre)
Solution to the Wave function for a H-
atom
Any wave function Ψ can be divided into two components

Rnl(r) Ylm(,)

radial Ψ angular Ψ

Rnl(r) Ylm(,)

Where a0 = Bohr radiusFor all s orbitals

(constant) = 52.9(1s,
pm 2s, 3s, etc,) Y is a constant.
Shape of an s-orbital
 The shape of an s-orbital is spherically symmetrical, independent of  and
.

Figure 1.23 Chem Principles

Probability Density Plots of s-orbitals

2a0

Figures from MIT OCW

NODE a value of r,  and  for which both  and 2 = 0

RADIAL NODE: a value of r for which both  and 2 = 0
Radial Nodes = n - 1 - l
For 1s radial nodes = 1 – 1 – 0 = 0
For 2s radial nodes = 2 – 1 – 0 = 1
For 3s radial nodes = 3 – 1 – 0 = 2
How many radial nodes does a hydrogen atom 3d
orbital have?

1. One
2. Two
3. Three
4. Four
5. Five
6. Six
7. Seven
8. Eight
9. Zero
 Radial Probability Distribution
 The probability of finding an electron in a shell of thickness dr at a distance r
from the nucleus.

For s-orbitals RPD = 4πr22 dr

rmp
= Bohr radius = 0.529Å

http://www.emu.edu.tr/mugp101/PHYSLETS/physletprob/ch10_modern/radial.html
RPD for a 2s and a 3s orbital for H-
atom:
volume

rmp = 11.5a0
rmp = 6a0

node node
node

as n increases rmp also increases.

Concept Check
 Identify the correct RPD plot (and radial node number) for a 4s
orbital

1. 3.

2. 4.
Radial Probability Distributions for
other orbitals:

<

3d 3p 3s
Quantum Tunneling

Scanning Tunneling Microscope

 Scanning Tunneling Microscopy
(STM)
• Atoms can be arranged and imaged!
Photos produced from
the work of C.P. Lutz,
Zeppenfeld, and D.M.
Eigler. Reprinted with
permission from
International Business
Machines Corporation,
copyright 1995.

Carbon monoxide Iron atoms arranged

molecules arranged on a copper (111)
on a platinum (111) surface. These Kanji
surface. characters represent
the word “atom”.

61
p-orbitals (l = 1):
 For any sub-shell l = 1 there are three p orbitals;
 m = +1 or -1 (px or py) and m = 0 (pz)
 Difference from the s-orbitals lies in the fact that p-orbitals wave-functions
depend on  and .

p-orbitals are not spherically symmetrical!

p and d-orbitals
p-orbitals look like a dumbell with 3 orientations: px, py, pz (“p sub z”).

p-orbitals consist of two lobes seperated by a nodal plane.

There is zero probability of finding a p-electron at the nucleus.

Only electrons in the s orbitals have a substantial probability of being very close
to the nucleus

Electrons in the s orbitals are LEAST shielded.

 d-orbitals
Four of the d orbitals resemble two dumbells in a clover shape.

The last d orbital resembles a p-orbital with a donut wrapped around the middle!
Multi-Electron Atoms and the spin
quantum number ms
When the Schrodinger wave equation is solved for multielectron atoms, a fourth
quantum number ms the spin quantum number also appears.

ms = +1/2 (spin up) or ms = -1/2 (spin down)

ms completes the description of an electron and is NOT dependant on the orbital.

Discovery of Electron Spin:

Ne
1s2 2s2 2px2 2py2 2pz2
Uhlenbeck and Goudsmit

http://www.ilorentz.org/history/spin/goudsmit.html
Wolfgang Pauli
Pauli Exclusion Principle
 No two electrons in the same atom can have the same four quantum
numbers.
 The Pauli exclusion principle limits us to two electrons per orbital.

Ne
1s2 2s2 2px2 2py2 2pz 2
Concept Check!
 How many electrons in a single atom can be in a 2p state?

1. one
2. two
3. three
4. four
5. five
6. six
7. seven
8. eight
9. zero