Quantum model

2 Lecture 2

Objectives or Aims
At the end of this unit you should be able to;
(a) explain the dual nature of matter and wave
(b) describe qualititatively the Schrödinger equation and the
quantum numbers
(c) draw the shapes of atomic orbitals
(d) explain the Pauli’s exclusion principle and write electronic
configuration

2.0 Introduction
In this lecture, we will see that to explain phenomena at atomic and molecular level, classical
physics is inadequate, only the quantum theory will do. This Lecture describes the current
quantum model of an atom. Though, the concept requires knowledge of some mathematics and
physics, we will explain it, without rigorously solving those equations.

In high school you learnt electronic configuration of atoms.

 The electrons are arranged in energy levels, labeled n=1, 2, 3, 4 etc.
 That the maximum number of electrons in each energy level is given by 2(n) 2.
o The first energy level can have a maximum of 2(1)2=2
o The second energy level can have a maximum of 2(2)2=8
o The third energy level can have a maximum of 2(3)2=18
o And so on
No explanation was given at that time.
2.1.0 Quantum Model of an Atom
Our current understanding of the electronic structure of an atom is expressed in terms of
quantum mechanics. A fundamental concept of quantum mechanics is that all matter has wave
and particle-like properties.

2.1 De Broglie Equation- Dual Nature of Matter

Physicists were mystified but intrigued by Bohr’s theory. They questioned why is the electron in
Bohr atom restricted to orbiting the nuclear at fixed distances? In 1924 the French physicist
Louis de Broglie provided a solution to this puzzle. De Broglie reasoned as follows: If light
waves can behave like a stream of particles (photons), then perhaps particles such as electrons
posses wave properties.

•Light can behave both as a wave and as particles (photons). Likewise all matter (e.g., electrons,
protons & neutrons) can also behave as waves.

From Einstein relativity theory, the fundamental law relating energy E, rest mass m0 and
momentum p of a particle is

2
E
   p  m0 c
2 2 2

c

E
The rest mass of a photon is zero, so m0=0 and therefore momentum is p 
c

From Plank’s quantum theory

E  h
Therefore E  h  mc
2
But p=mc

h h
p  mc  
c 

h
Implying 
p

= wavelength of the moving particle;

h: Planck's constant 6.626 x 10-34 J.s

m: mass of the moving particle.

That is, all particles in motion have a wavelength that depends on the particle’s momentum. The
larger the momentum, the smaller the wavelength.

•In 1927, Davisson and Germer at Bell Laboratories showed that when a beam of electrons was
directed at a nickel crystal, a diffraction pattern was observed.

2.2 Heisenberg Uncertainty Principle

Due to the dual nature of matter, both particles and wavelike properties, it is impossible to
simultaneously determine both the position and momentum of an object especially as small as an
electron. The position and momentum of a particle cannot be simultaneously measured with high
precision. There is a minimum for the product of the uncertainties of these two measurements.
There is likewise a minimum for the product of the uncertainties of the energy and time.

h
xp 
2
Where Δx = uncertainty in position
 Δp = uncertainty in momentum

This is not a statement about the inaccuracy of measurement instruments, nor a reflection on the
quality of experimental methods; it arises from the wave properties inherent in the quantum
mechanical description of nature. Even with perfect instruments and technique, the uncertainty is
inherent in the nature of things.

2.3 Wave-Like Property of an Electron

•An electron in an atom is viewed as a standing wave. Some common examples of standing
waves are: a string attached at both ends to produce a musical tone in a guitar and violin.

Figure 2.1 standing wave

We use the mathematical function Ψ (Greek Psi), called wavefunction to describe the wave-like
behavior of an electron in a region of space called the atomic orbital.
  Ψ has positive and negative amplitudes, like any wave.

Figure 2.2

 Due to the wave-like behavior of an electron, we cannot pin down its position and
momentum at the same time (Heisenberg Uncertainty Principle).
 In other words, we do not know the exact location of an electron and how it moves from
one spot to another in an atom.
 Instead, we can only speak of the probability of finding an electron in a given volume
of space. This is given by the function Ψ2.

2.4 Schrödinger Wave Equation

 Based on the wave-particle dual nature of electron, Schrödinger developed a partial

differential equation to describe the behavior of an electron around an H atom. He received
Nobel Prize in 1933.

 2ψ  2ψ  2ψ 8π 2 m
   E  V ψ  0
x 2 y 2 z 2 h2
Schrödinger equation for a hydrogen atom
 This equation shows the relationship between the wave function of the electron Ψ, and E
and V, the total and potential energies of the system, respectively. The derivation of this equation
is beyond the scope of this course (will be derived in SCH 200).

 There are many solutions to the Schrödinger's equation. Each solution is represented by
the wavefunction, Ψ, which describes an atomic orbital. The Uncertainty Principle tells us that
we cannot pin down the exact location and momentum of an electron at the same time. So
chemists speak of "electron cloud" or electron density around a nucleus.

 An atomic orbital, is defined as the boundary surface, encloses 95% of the electron
density for a particular wavefunction Ψ. Each atomic orbital (Ψ) may be uniquely defined by a
set of three quantum numbers:

n (the principal quantum number);

l (the orbital angular quantum number) and
ml (the magnetic quantum number).

 Since electron behaves as if it is spinning about an axis, a spin quantum number m s is

also required to uniquely described an electron in an atomic orbital.

Figure 2.2 Spinning electron

 2.5 Quantum Numbers and their Properties

Symbol Name Allowed Properties

Values

N Principal n = 1, 2, 3, 4,  determines the size and energy of an atomic orbital

Quantum ...
 As n increases, the number of allowed orbitals
Number
increases, the size and energies of those orbitals also
increase.

L Orbital l = 0, 1, 2, ...,  Describe the shape of an atomic orbital

Quantum n-1
Number

ml Magnetic ml = -l, ..., -(l-  Describe the directionality of an atomic orbital

Quantum 1), 0, 1, 2, ...
Number +l

ms Spin ms = - ½, + ½  Describes the orientation of the electron spin in space

Quantum
Number

Orbitals with different l values are known by the following labels:

l 0 1 2345…

Label s p dfgh…
Allowed values enable us to know the maximum number of electrons in each energy level

n l ml and ms
1 0 0
↑↓ 2 electrons in 1s orbital
Total of 2 electrons in the
first energy level
2 0 0
↑↓ 2 electrons in 2s orbital
1 -1 0 1
↑↓ ↑↓ ↑↓ 6 electrons in 2p orbital
Total of 8 electrons in the
first energy level; 2 in s
orbital and 6 in p orbitals
3 0 0
↑↓ 2 electrons in 3s orbital
1 -1 0 1
↑↓ ↑↓ ↑↓ 6 electrons in 3p orbital

2 -2 -1 0 1 2
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ 10 electrons in 3d orbital
Total of 18 electrons in the
first energy level; 2 in s
orbital, 6 in p orbitals and
10 in d orbitals

Activity

Using the same argument, show the maximum number of electrons for n=4.
2.5.1 Relationship between quantum numbers and atomic orbitals
There is a relationship between the quantum numbers and the atomic orbitals, ml. When l=0,
(2l+1)=1, and there is one value of ml; thus we have an s orbital. When l=1, (2l+1)=3, so there
are three values of ml; or three p orbitals, labeled px, py, and pz. When l=2, (2l+1)=5, and there
are five values of ml, and corresponding five d orbitals are labeled with more elaborate
subscripts. This is shown in the table 2.5.1 below.

n l ml Number of Atomic orbitals

orbitals Designation
1 0 0 1 1s

2 0 0 1 2s
1 -1 0 1 3 2px, 2py, 2pz

3 0 0 1 3s
1 -1, 0, 1 3 3px, 3py, 3pz
2 -2,-1, 0, 1,2 3 d xy , 3d yz , 3d xz , 3d x 2  y 2 , 3d z 2

    
    

2.5.2 Electron Coordinates

The four quantum numbers n, l, ml and ms enable us to label completely an electron in any orbital
in any atom. For example, the four quantum numbers for a 2s orbital electron are n=2, l=0, ml=o
and either ms=+½ or ms=-½. In practice it is inconvenient to write out all the individual quantum
numbers, and so we use the simplified notation (n, l, ml, ms). For the example above, the
quantum numbers are (2, 0, 0, +½) or (2, 0, 0, -½). The value of ms has no effect on the energy,
size, shape, or orientation of an orbital, but it plays a profound role in determining how electrons
are arranged in an orbital.
2.5.3 The Pauli Exclusion Principle
This principle states that no two electrons in an atom can have the same four quantum
numbers. If two electrons in an atom should have the same n, l and ml values (that is, these two
electrons are in the same orbital), then they must have different values of ms. In other words,
only two electrons may exist in the same atomic orbital, and these electrons must have
opposite spins.

Consider the helium atom, which has two electrons. The three possible ways of placing two
electrons in the 1s orbital are as follows:

↑↑ ↓↓ ↑↓
1s2 1s2 1s2
(a) (b) (c)

Diagram (a) and (b) are ruled out by the Pauli Exclusion Principle. In (a), both electrons have
the same upward spin and would have the quantum numbers (1, 0, 0, +½); in (b), both electrons
have the downward spin and would have the quantum numbers (1, 0, 0, -½). Only the
configuration in (c) is physically acceptable, because one electron has quantum numbers (1, 0, 0,
+½) and the other has (1, 0, 0, -½). Thus the helium atom has the following configuration:

He ↑↓
1s2
Note that 1s2 is read “one s two”, not “one s squared”.

SELF-TEST QUESTIONS

i) List the different ways to write the four quantum numbers that designate an electron
in a 3p orbital.
 ii) List the different ways to write the four quantum numbers that designate an electron
in a 5d orbital

2.6 Pictorial Representation of Atomic Orbitals

 An atomic orbital is defined as a boundary surface which encloses 95 % of the electron

density for a particular Ψ.
 Atomic orbitals can be represented pictorially by boundary surface diagrams (H&S Fig.
2.7.1, 2.7.2, 2.7.3) or electron density contour plots (see overhead).

s orbitals
 l = 0, ml = 0, the angular wavefunction A( , ) is independent of the angle q and f .
Therefore, an s orbital is spherically symmetrical about the nucleus.

Figure 2.7.1 Boundary surface diagram of an s orbital. (Figure taken from Shriver &
Atkins)

In two dimensions it is represented as:

 z

s orbital

p orbitals
 l = 1; ml = -1, 0, + 1. 3 possible orientation of p orbitals: along the x, y and z axes.
 Dumb-bell shaped; electron density concentrated in identical lobes on either side of the
nucleus.
 pz orbital has an angular node [ A( , )  0 ] along the xy plane; px orbital has an angular
node along the yz plane; py orbital has an angular node along the xz plane.
 The electron density contour map shows that there is no radial node for the 2p orbitals but

1 radial node for the 3p orbitals. [see example 1]

Figure 2.7.2 Boundary surface diagram of p orbitals. The lightly shaded lobe has a positive
amplitude; the more darkly shaded lobe is negative (Figure taken from Shriver
& Atkins).

In two dimensions they are represented as:

 z
z
z

+
-
y - + y y
+
x - x x

pz py px

d orbitals

 l = 2, ml = -2, -1, 0, + 1, 2. There are five d orbitals.

 dxy, dyz, dxz, dx2-y2 have clover leaf shape and have 4 lobes of maximum electron
probability centered in the plane indicated in the orbital label. The four lobes are separated by
two nodal planes through the nucleus.
 dxy, and dx2-y2 are both centered in the xy plane while the lobes of dxy lie between
the axis.
 dz2 has two lobes along the z axis and a "belt" centered in the xy plane.
Figure 2.7.3 Boundary surface diagram of d orbitals. The lightly shaded lobe has a positive
amplitude; the more darkly shaded lobe is negative (Figure taken from Shriver &
Atkins).

In two dimensions they are represented as:

 y z
z

-
x - x y

dxz
dxy dyz

y
z

dx2-y2
dz2

The shaded lobe has a positive sign

Note the labelling of the axes

2.7 Electronic Configuration

2.7.1 Energy Levels in Hydrogen and Other Atoms

1 For H, the energy of the electron only depends on n, principal quantum number. The
s, p, d, f orbitals have the same energy.
2 In the ground state, the electron in the H atom resides on the 1s orbital.
3 For other atoms with more than one electron, electron-electron repulsion and
shielding play a role so energy depends on angular momentum quantum number l
as well as the principal quantum number n. The energies of the atomic orbitals in
multielectron atoms are arranged in the order:

ns < np < nd < n f

Figure 2.9.1. Orbital energy level diagrams for a hydrogen atom and multielectron atoms
(diagram taken from McMurry & Fay).
Electronic Configurations
•Describe how electrons distribute themselves in various orbitals in an atom.

We will learn the rules used in writing electron configurations for the elements. The process is
based on the Aufbau principle (The German word Aufbau means ‘building up’)

2.9.2 Aufbau Principle

 A set of rules guiding the filling order of orbitals.

1 Fill in electrons in the lowest energy orbital first.

2 Only two electrons with opposite spins per orbital (because Pauli exclusion principle says
that no two electrons in an atom can have the same four quantum numbers).
3 If two or more degenerate orbitals (i.e. orbitals with the same energy) are available,
electrons go into each degenerate orbital with parallel spins until the orbitals are half-fill
(Hund's rule).

2.7.3 Order of Orbital Filling in Poly-electronic Atoms:

Figure 2.9.3 The order in which atomic orbitals are filled in a many electron atoms.
Start with the 1s orbital and move downward, following the direction of the arrows. Thus the
order goes as follows 1s→2s→2p→3s→3p→4s→3d→4p→5s→4d….

The Ground State Electron Configuration of the Elements*

Atomic Atom Electronic Atomic Atom Electronic Atomic Atom Electronic configuration
number configuration number configuration number
1 H 1s1 38 Sr [Kr]5s2 74 W [Xe]6s14f145d5
2 He 1s2 39 Y [Kr]5s24d1 75 Re [Xe]6s24f145d5
3 Li [He]2s1 40 Zr [Kr]5s24d2 76 Os [Xe]6s24f145d6
4 Be [He]2s2 41 Nb [Kr]5s24d3 77 Ir [Xe]6s24f145d7
5 B [He]2s22p1 42 Mo [Kr]5s14d5 78 Pt [Xe]6s14f145d9
6 C [He]2s22p2 43 Tc [Kr]5s24d5 79 Au [Xe]6s14f145d10
7 N [He]2s22p3 44 Ru [Kr]5s24d6 80 Hg [Xe]6s24f145d10
8 O [He]2s22p4 45 Pd [Kr]5s24d7 81 Tl [Xe]6s24f145d106p1
9 F [He]2s22p5 46 Ag [Kr]5s24d8 82 Pb [Xe]6s24f145d106p2
10 He 1s22s22p6 47 Ag [Kr]5s14d10 83 Bi [Xe]6s24f145d106p3
11 Na [Ne]3s1 48 Cd [Kr]5s24d10 84 Po [Xe]6s24f145d106p5
12 Mg [Ne]3s2 49 In [Kr]5s24d105p1 85 At [Xe]6s24f145d106p5
13 Al [Ne]3s23p1 50 Sn [Kr]5s24d105p2 86 Rn [Xe]6s24f145d106p6
14 Si [Ne]3s23p2 51 Sb [Kr]5s24d105p3 87 Fr [Rn]7s1
15 P [Ne]3s23p3 52 Te [Kr]5s24d105p4 88 Ra [Rn]7s2
16 S [Ne]3s23p4 53 I [Kr]5s24d105p5 89 Ac [Rn]7s26d1
17 Cl [Ne]3s23p5 54 Xe [Kr]5s24d105p6 90 Th [Rn]7s26d2
18 Ar [Ne]3s23p6 55 Cs [Xe]6s1 91 Pa [Rn]7s25f26d1
19 K [Ar]4s1 56 Ba [Xe]6s2 92 U [Rn]7s25f36d1
20 Ca [Ar]4s2 57 La [Xe]6s25d1 93 Np [Rn]7s25f46d1
21 Sc [Ar]4s23d1 58 Ce [Xe]6s24f15d1 94 Pu [Rn]7s25f6
22 Ti [Ar]4s23d2 59 Pr [Xe]6s24f3 95 Am [Rn]7s25f7
23 V [Ar]4s23d3 60 Nd [Xe]6s24f4 96 Cm [Rn]7s25f76d1
24 Cr [Ar]4s13d5 61 Pm [Xe]6s24f5 97 Bk [Rn]7s25f9
25 Mn [Ar]4s23d5 62 Sm [Xe]6s24f6 98 Cf [Rn]7s25f10
26 Fe [Ar]4s23d6 63 Eu [Xe]6s24f7 99 Es [Rn]7s25f11
27 Co [Ar]4s23d7 64 Gd [Xe]6s24f75d1 100 Fm [Rn]7s25f12
28 Ni [Ar]4s23d8 65 Tb [Xe]6s24f9 101 Md [Rn]7s25f13
29 Cu [Ar]4s13d10 66 Dy [Xe]6s24f10 102 No [Rn]7s25f14
30 Zn [Ar]4s23d10 67 Ho [Xe]6s24f11 103 Lr [Rn]7s25f146d1
31 Ga [Ar]4s23d104p1 68 Er [Xe]6s24f12 104 Unq [Rn]7s25f146d2
32 Ge [Ar]4s23d104p2 69 Tm [Xe]6s24f13 105 Unp [Rn]7s25f146d3
33 As [Ar]4s23d104p3 70 Yb [Xe]6s24f14 106 Unh [Rn]7s25f146d4
34 Se [Ar]4s23d104p4 71 Lu [Xe]6s24f145d1 107 Uns [Rn]7s25f146d5
35 Br [Ar]4s23d104p5 72 Hf [Xe]6s24f145d2 108 Uno [Rn]7s25f146d6
36 Kr [Ar]4s23d104p6 73 Ta [Xe]6s24f145d3 109 Une [Rn]7s25f146d7
37 Rb [Kr]5s1

*The symbol [He] is called the helium core and represents 1s2. [Ne] is called the neon core and
represents 1s2s2p6. [Ar] is called the argon core and represent [Ne]3s23p6. [Kr] is called the
krypton core and represents [Ar]4s23d104p6. [Xe] is called the xenon core and represents
[Kr]5s24d105p6. [Rn] is called the radon core and represents [Xe]6s24f145d106p6.