Classical to Quantum Mechanics

Wave nature of particles: de Broglie hypothesis (1923)

de Broglie proposed that just as light shows both wave and particle
aspects, matter also has a “dual” nature.

de Broglie relation:

• The de Broglie wavelength of an electron moving at 1.0 x 106 m/s is

• For a macroscopic particle of mass 1.0 g moving at 1.0 x 106 cm/s

Quantum effects are unobservable for the motion of macroscopic objects !

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 Classical to Quantum Mechanics
Wave nature of particles

A beam of particles passing through two

slits produces two smaller beams of
particles

When a beam of electrons goes through

two closely spaced slits, they create an
interference pattern => Wave Nature

The wave nature of the electron is an

inherent property of individual electrons

Superposition of waves
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 Classical to Quantum Mechanics
Schrödinger’s cat

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 Classical to Quantum Mechanics
Schrödinger’s cat

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 Classical to Quantum Mechanics
Schrödinger’s cat

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 Quantum Mechanics
Uncertainty Principle
! In classical physics, we can calculate, with great accuracy, a particle’s position, direction of
motion, and speed at any instant.
! Can we do the same for an electron, which exhibits wave properties?
! A wave extends in space, and its location is not precisely de ned. We can then anticipate that it
is impossible to determine exactly where an electron is located at a speci c instant.

! Heisenberg proposed that “It is impossible to specify simultaneously, with arbitrary precision, both
the momentum (p) and the position (x) of a particle.”

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 Quantum Mechanics
Uncertainty Principle ∆x m∆v ≥ h/4π
• Suppose the speed of a projectile of mass 1.0 g is known to within 1 μms−1. The minimum
uncertainty in its position is

• The electron has a mass of 9.11 x 10-31 kg and moves at an average speed of about 5 x 106 ms-1 in
a hydrogen atom. Let’s assume that we know the speed to an uncertainty of 1% [i.e, an
uncertainty of (0.01)(5 x 106 ms-1) = 5 x 104 ms-1]. The uncertainty in the position of the electron is

The diameter of a hydrogen atom is about 1 x 10-10 m, the ∆x of the electron in the atom is an
order of magnitude greater than the size of the atom.
Thus, we have essentially no idea where the electron is located in the atom.
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transition states of chemical
reactions using femtosecond
spectroscopy"

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 Quantum Mechanics
The Schrödinger Equation (SE)

Time-independent Schrodinger Equation (TISE)

is a mathematical operator

KE PE

Time-dependent Schrodinger Equation (TDSE)

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 Quantum Mechanics
The Time Independent Schrödinger Equation (TISE)
For a system (1 particle) de ned in 1-dimension (1D)

can be complex or real function

• SE is a partial differential equation

• Eigenvalue equation
Operator × function = scalar quantity × original function
Eigenvalue Eigenfunction
For a system ( 1 particle) de ned in 3-dimension (3D)

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 Quantum Mechanics
The Born interpretation of the wavefunction
• The wavefunction is simply an amplitude
• It is the square of the wavefunction that is meaningful
• | |2 = * is the probability density => (a+ib)*(a+ib)=(a-ib)(a+ib)
• is the probability amplitude
• Stationary state – probability density does not change with time
If the wavefunction of a particle has the value ψ at some point r, then, the
probability (P) of nding the particle in an in nitesimal volume dτ = dxdydz
at that point is

P = | |2 dτ

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https://www.nobelprize.org/ 26
 Quantum Mechanics
Acceptable wavefunctions
For a normalized function N , the probability of the particle somewhere is 1.

Requirements of an acceptable wavefunction.

• The wavefunction should possess the following conditions

• Single-valued
• Wavefunction and its rst derivative - continuous
• Finite everywhere
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 − 2 = Eψ(x)
∙ when n = 2, there are8πtwo m maxima
dx2 at L/4 and 3L/4 and there is
one node;
or

Quantum Mechanics
316 ∙ a wave
Chapter 7 • Quantum 316 functionand
Theory has Atomic
Chapter
2
n – 71 •nodes
Structure
Quantum
2
and nTheory
maximumandprobability
Atomic Structure
al densities; and d ψ(x) 8π mE
2
= − 2 ψ(x)
∙ the number of nodes dx and the numberh of maximum probability
densities describes
both increase
so that
as energywhose
increases.
so that
Thus, the equation a function second derivative is the function

ψ(x) = A sin kx = A sin[( ψ(x) 2 ) ] kx = A sin[(

The Particle-in-a-box Model

Ψ2(x)
Ψ(x)

Ψ(x)
8π2mE 1/2 8π2

Energy
multipliedAnby interesting
a negative
Nodes constant.
point to The trigonometric
notice is+ sine
Nodes
that the function
wave is a possible
functions in + solu-
tion to this equation: = A xsin
Figure 7.18 look very
Consider a particle con ned in a 1D boxmuch like the allowed wavelengths for a + h+ Ψ h
0 0 E Ψ 2
plucked guitarψ(x)
string
= A(see
sin Figure
kx
– 7.12).
– – – –
3
– –
3 3

where A and
Since the potential energy becomes
are constants. Substituting the sine
Since theinfinite
potential
outside
energythebecomes
box, theinfinite
probability
outside
of ft
The k Schrödinger Equation for the function
Hydrogen Atom The
the particle there is
the0,H that
atomtheis, particle
ψ(x)=∞ = 0 there
at x is= V0, 0= and
that xis,=ψ(x)
0Therefore,
L. = 0 at x = 0 an

Energy
0
in place ofSchrödinger
ψ(x) in the equation
simplified Schrödinger
can equationforgives
be solved exactly because Vx x V=∞
inside the box

[( h ) ] [( h )
A it has
A 2 only
waveone electron and,
2
8π mE
function
Athus, no
A electron-electron
wave for interactions.
a function
particle 2
for 1/2
a particle B 2 The 1/2
d
[A sin (kx)] =− A sin (kx) 8π mE 8π mE
Hydrogen’s
in
dx2
aelectron can hbe2 thought in
one-dimensional of as similar ψ(L)
to the particle
a one-dimensional systemin=a A sin
2
Lψ(L)= 0= A sin
system
2
of t
box, in that it is confined to a small volume by its attraction to the +
Solving for k gives
nucleus. However, unlike the particle in a box, the electron does have E2 – Ψ2 x Ψ2
2

Noting that Moreover,

sin(x) = the 0 only Noting
when can that
x is xsin(x)
a= 0multiple
= 0 only of π xwhen
(that is,
x issina [nπ]
multiple= 0)o
k = ( 2 that
h ) x, y, and z, not just one. Figure
=L
potential energy due 8π2to
mEthat1/2
attraction. electron
move in three dimensions, that
7.17 The particle +
E1 in a box model. Ψ1 Ψ21
The Schrödinger equation for a single electron moving in three

( 2 ) ( n2 = )
2 1/2 Wave functions2 1/2 Probability densities
dimensions and attracted to a nucleus is 8π mE 8π mE
L =Figure
nπ 7.18where Wave functions1,(ψ)2,and
L3,=probability
...nπ densities
where n
h h levels of a particle in a one-
8π2me [ dx2 ]
2 2 2 2
A possible solution, h dψ dψ dψ (ψ2
) for the first four energy
− + + 2 2
+ V(x, y, z)ψ = Eψ
Solving
dz for the energy, E , of dimensional
a box.
n Solving for theatenergy,
the particle particular
En, ofvalue
the particle
of n gives
at a the
particul
follo
dy

n2h2 n2h2
En = n = 1, 2, 3, E...n = n = 1, 2,
Solving for k gives,
8mL2 8mL2

Notice that since n has only

Notice
discrete
that(integer)
since n has
values,
onlythe
discrete
energy(integer)
of the particle
values
28
also have discrete values; also
thus,have
we say
discrete
that the
values;
energy
thus,
of we
the say
particle
that the
is qua
ene
fi
 ψ(x) = A sin kx = A sin[( 2 ) x ]
8π2mE 1/2
Quantum Mechanics
h
e potential energy becomes infinite outside the box, the probability of finding
cle thereThe
is 0,Particle-in-a-box
that is, ψ(x) = 0 atModel
x = 0 and x = L. Therefore,

[( h2 ) ]
8π2mE 1/2
ψ(L) = A sin L =0

hat sin(x) = 0 only when x is a multiple of π (that is, sin [nπ] = 0) means

( h2 ) L = nπ
8π2mE 1/2
where n = 1, 2, 3, ...

for the energy, En, of the particle at a particular value of n gives the following:

n2h2
En = n = 1, 2, 3, ... (7.8)
8mL2

hat since n has only discrete (integer) values, the energy of the particle must
ve discrete values; thus, we say that the energy of the particle is quantized,
values of n are called quantum numbers. (We discuss quantum numbers fur-
er in the section.) The difference in energy between a level with quantum 29
n and one with quantum number n + 1 is
 expression for A into the wave function gives
Quantum Mechanics
ψn (x) = √ sin(
L )
2 nπx
n = 1, 2, 3, ...
hapter The
7 • Quantum TheoryModel
Particle-in-a-box and Atomic Structure L
• Boundary conditions result in quantization
An examination of the wave functions and the probability densi
• Each dimension, gives one so that number
quantum
• (n-1) nodes for the first four En values are shown in Figure 7.18. Note that
sin[( at
• Energy increases with number of nodes 2 8π
∙ when n = 1, the maximum probability
ψ(x) =density ψ =(x)Aoccurs
A sin kx
• Zero-point energy:
and there
Lowest energy possible (n=1) are no nodes;
∙ when nSince = 2, the
there are twoenergy
potential maximabecomes
at L/4 and 3L/4 outside
infinite and ther
one node;
• Energy difference between the particle
two levels, there
n and n+1 is 0, that is, ψ(x) = 0 at x = 0 an
∙ a wave function has n – 1 nodes and n maximum 2probabi

[( hprobabi
2 )
1/2
densities; and 8π mE
ψ(L) = A sin
∙ the number of nodes and the number of maximum
densities both increase as energy increases.
Noting that sin(x) = 0 only when x is a multiple o
that point to notice is that the wave functions
An interesting
Figure 7.18 look very much like 2the allowed
1/2 wavelengths
30
fo
8π mE
 Quantum Mechanics
The Particle-in-a-box Model: The electronic absorption spectra of polyenes

Using an effective box length of 18.3 Å, we

get = 480 nm

33
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