2.QM Theory Motion Rev16

QUANTUM THEORY
Techniques and applications

Key points
2
 To calculate the properties of systems >>> solve the appropriate

Schrödinger equation.
 the essentials of the solutions for three basic types of motion:
translation, vibration, and rotation >> they are ways in which
molecules store energy.
 Only certain wavefunctions and their corresponding energies are
acceptable.
 Quantization emerges as a natural consequence of the equation and
the conditions imposed on it.
 The solutions bring to light a number of nonclassical features of
particles, especially their ability to tunnel into and through regions
where classical physics would forbid them to be found.
 We also encounter a property of the electron, its spin, that has no
classical counterpart.
QM Theory Dwi Hudiyanti  2016 4/5/2018

Translational motion
 Free motion in one
dimension
 all values of k, and
therefore all values of
the energy, are
permitted.
 the translational energy
of a free particle is not
quantized.
 if the momentum is
certain, then the position
cannot be specified

3
A particle in a box
The acceptable solutions
 the acceptable
wavefunctions must satisfy
certain boundary
conditions
 the boundary conditions
are ψk(0) = 0 and ψk(L)
= 0.
 only certain wavefunctions
are acceptable
 restricts observables to
discrete values
QM Theory Dwi Hudiyanti 2016 4/5/2018
4
The acceptable solutions
 boundary conditions
 the wavefunction must be zero
where V is infinite, at x < 0
and x > L.
 The continuity of the
wavefunction then requires it
to vanish just inside the
 well at x = 0 and x = L.
 the boundary conditions are
ψk(0) = 0 and ψk(L) = 0.
 These boundary conditions
imply energy quantization

5
the need to satisfy boundary conditions implies that
only certain wavefunctions are acceptable, and
hence restricts observables to discrete values.

6
The properties of the solutions
 the value of C that

ensures that the integral
of ψ 2 over all the
space available to the
particle (that is, from x
= 0 to x = L) is equal to
1
7
Energies of a
particle in a box
Wavefunctions of
a particle in a box

8
9
 The energies and wavefunctions are labelled with

the ‘quantum number’ n.
 A quantum number is an integer that labels the state
of the system.
 For a particle in a box there is an infinite number
of acceptable solutions, and the quantum number n
specifies the one of interest

Some of the wavefunctions of a
particle in a box
 All are sine functions with the same
maximum amplitude but different
wavelengths.
 Shortening the wavelength >>> a
sharper average curvature of the
wavefunction >>> an increase in the
kinetic energy of the particle.
 the number of nodes (points where the
wavefunction passes through zero) also
increases as n increases
 the wavefunction ψn has n − 1 nodes.
 Increasing the number of nodes >>>
increases the average curvature of the
wavefunction >>> the kinetic energy of
the particle.
10
The linear momentum
 not well-defined because the
wavefunction sin kx (like cos
kx) is not an eigenfunction of
the linear momentum
operator.
 each wavefunction is a  Opposite directions of travel
superposition of momentum with equal probability
eigenfunctions  a particle in a box rattles
 the value: from wall to wall
 in any given period spends
half its time travelling to the
left and half travelling to the
right.

11
Zero-point energy of
a particle in a box
 the uncertainty principle  if the wavefunction is to
requires a particle to be zero at the walls, but
possess kinetic energy smooth, continuous, and
if it is confined to a not zero everywhere,
finite region: the then it must be curved,
location of the particle and curvature in a
is not completely wavefunction implies the
indefinite, so its possession of kinetic
momentum cannot be energy.
precisely zero. Hence it
has nonzero kinetic
energy.
12
The separation between adjacent
energy levels
 quantum numbers n and n

+1  Atoms and molecules free
 The separation decreases to move in normal
as the length of the laboratory-sized vessels
container increases >> may therefore be treated
very small when the as though their
container has macroscopic translational energy is not
dimensions. quantized. The
 The separation of translational energy of
adjacent levels becomes completely free particles
zero when the walls are (those not confined by
infinitely far apart. walls) is not quantized.

13
The probability density for a particle
in a box
 varies with position
 ψ2(x) becomes more uniform as n
increases.
 reflects the classical result that a
particle bouncing between the walls
spends equal times at all points.
 corresponds to the classical prediction
at high quantum numbers is an
illustration of the correspondence
principle,
 classical mechanics emerges from
quantum mechanics as high quantum
numbers are reached.

14
15
Two dimensions motion
 The wavefunction is
now a function of both
x and y

16
Separation of variables

17
Wavefunctions and energies of a
particle in a two-dimensional box

18
19
Degeneracy
20
 a two-dimensional box, L1 = L2 = L.
although the wavefunctions are

different, they are degenerate,
meaning
that they correspond to the same
energy
there are two degenerate
wavefunctions, we say that the
energy level 5(h2/8mL2) is ‘doubly
degenerate’
21

Tunnelling
 the probability of
tunnelling of a particle of
mass m incident on a finite
barrier from the left
 x < 0, V = 0
 0 ≤ x ≤ L, V = V
real
functions

22
 x > L, V = 0

23
Transmission probability
24
 Transmission`probability for κL >> 1

 The transmission
probability decreases
exponentially with the
thickness of the barrier
and with m½.
 particles of low mass are
more able to tunnel
through barriers than
heavy ones

25
Questions ???

26
Quiz !!!
 Self-test 7.6
 Self-test 7.10
 Self-test 8.4

27
VIBRATIONAL MOTION
Hooke’s law
Potential energy
Parabolic
potential energy
The Schrödinger equation

for the particle undergo a
harmonic
oscillation
29

The energy levels
 Quantization of Energy levels of a harmonic
energy levels >>> oscillator
the boundary
conditions: the
oscillator will not be
found with infinitely
large displacements
from equilibrium,
 the only allowed
solutions
30

the separation between adjacent levels
 The energy separation

is negligibly small for
macroscopic objects
(with large mass), but
is of great importance
for objects with mass
similar to that of
atoms.
31

Zero-point energy of a harmonic oscillator
 the smallest permitted  v cannot take negative

value of v is 0 values, for if it did the
wavefunction would be ill-
behaved
 the particle is confined, its
position is not completely
uncertain, and therefore
 one in which the particle its momentum, and hence
fluctuates incessantly its kinetic energy, cannot
around its equilibrium be exactly zero.
position; classical
mechanics would allow the
particle to be perfectly
still. 32

The wavefunctions
 the potential energy  the kinetic energy of
climbs towards infinity the oscillator depends
only as x2 and not on the displacement in
abruptly, the a more complex way
wavefunction (on account of the
approaches zero more variation of the
slowly at large potential energy), the
displacements than for curvature of the
the particle in a box. wavefunction also
varies in a more
complex way. 33

The form of the wavefunctions
Hv(y) is a Hermite polynomial
34

the wavefunction for the ground state (the
lowest energy state,
with v = 0) of the harmonic oscillator
that the probability density
35

 Both curves have their
largest values at zero
displacement (at x =
0),
 they capture the
classical picture of the
zero-point energy as
arising from the
ceaseless fluctuation of
the particle about its
equilibrium position. 36
note on the harmonic oscillator
wavefunctions
 The Gaussian function goes quickly to zero as the
displacement increases (in either direction), so all the
wavefunctions approach zero at large displacements.
 The exponent y2 is proportional to , so
the wavefunctions decay more rapidly for large masses
and large force constants (stiff springs).
 As v increases, the Hermite polynomials become larger
at large displacements (as xv), so the wavefunctions
grow large before the Gaussian function damps them
down to zero: as a result, the wavefunctions spread
over a wider range as v increases.
37

At high quantum numbers, harmonic
oscillator wavefunctions have
their largest amplitudes near the
turning points of the classical
motion (the locations at which V
= E, so the kinetic energy is
zero).
We see classical properties
emerging in the correspondence
limit of high quantum numbers,
for a classical particle is most
likely to be found at the turning
points (where it is briefly
stationary) and is least likely to
be found at zero displacement
(where it travels most rapidly).
38

The properties of oscillators
 the expectation values
of an observable Ω
the mean displacement, x
the oscillator is equally likely to be found on

either side of x = 0 (like a classical oscillator)
the mean square displacement, x2
corresponds to the classical amplitude of swing 39

increasing as the oscillator becomes more
highly excited QM Theory Dwi Hudiyanti 2016 4/5/2018
Virial
theorem
40

Tunnelling probabilities of Oscillators
???
 The probability of being found in classically forbidden
regions decreases quickly with increasing v, and
vanishes entirely as v approaches infinity, as we would
expect from the correspondence principle.
 Macroscopic oscillators (such as pendulums) are in states
with very high quantum numbers, so the probability that
they will be found in a classically forbidden region is
wholly negligible.
 Molecules, however, are normally in their vibrational
ground states, and for them the probability is very
significant.
41

42

ROTATIONAL MOTION
Rotation in two dimensions: a
particle on a ring
 The total energy is
equal to the kinetic
energy, because V = 0
everywhere.
not all the values of the angular

momentum are permitted in
quantum mechanics, and therefore
that both angular momentum and
rotational energy are quantized.
44

The qualitative origin of quantized
rotation
 the shorter the
wavelength of the
particle on a circular
path of given radius, the
greater the angular
momentum of the
particle.
 if we can see why the
wavelength is restricted
to discrete values, then
we shall understand why
the angular momentum is
quantized. 45

 The wavefunction reproduces itself on successive
circuits.
 Only some angular momenta are acceptable
 Only certain rotational energies exist.
 The energy of the particle is quantized.
 The only allowed wavelengths are
•ml, quantum number

•integral values including 0.
•ml = 0 corresponds to λ =∞; a
‘wave’ of infinite wavelength has a
constant height at all values of φ.
46

Angular momentum, Energy levels and
Wavefunctions of a particle on a ring
47

Quantization of rotation
 The energy is quantized
 Independent of the sense of rotation
 |ml | are doubly degenerate, except for ml = 0,
which is non-degenerate
 the angular momentum is quantized

48
 The increasing angular
momentum is associated
with the increasing
number of nodes in the
real and imaginary
parts of the
wavefunction
 the wavelength
decreases stepwise as
|ml | increases, so the
momentum with which
the particle travels
round the ring increases 49

Particle location Probability density
• independent of 
• the probability of locating the particle
on the ring is independent of 
• the location of the particle is
completely indefinite
• knowing the angular momentum
precisely eliminates the possibility of
specifying the location of the particle
• Angular momentum and angle are a
pair of complementary observables,
example of the uncertainty principle
50

Rotation in three dimensions: the
particle on a sphere
 rotating molecules and the
states of electrons in
atoms
 the wavefunction should
match as a path is traced
over the poles as well as
around the equator of the
sphere surrounding the
central point introduces a
second cyclic boundary
condition and therefore a
second quantum number
51

 The wavefunction is therefore

a function of the colatitude,
θ, and the azimuth,φ.
 particle confined to a
spherical surface, V = 0
Separation
of variables
52

 The acceptable  orbital angular
wavefunctions are momentum quantum
specified by two number l : non-
quantum numbers l negative, 2l + 1
and ml which are permitted values of
restricted to the values the magnetic quantum
number, ml.
 The normalized
wavefunctions >>>
the spherical harmonics
53

Energy levels and Angular momentum of a
particle on a sphere
 the energy is quantized  the number of nodes in
 independent of ml ψl,ml(θ,φ) increases with l
 a level with quantum number l  higher angular momentum
is (2l + 1)-fold degenerate implies higher kinetic energy,
a more sharply curved
wavefunction.
 the states corresponding to
high angular momentum
around the z-axis are those in
Magnitude of angular momentum
which the most nodal lines cut
the equator >>a high kinetic
energy arises from motion
parallel to the equator
because the curvature is
z-Component of angular momentum
greatest in that direction.
54

55
56
Space quantization
• If the angular momentum is

represented by a vector of length
proportional to its magnitude, to
represent correctly the value of the
component of angular momentum, the
vector must be oriented so that its
projection on the z-axis is of length
ml units
57

• the plane of rotation of
the particle can take
only a discrete range
of orientations
• the orientation of a
rotating body is
quantized.
space quantization
58

Spin
 Stern and Gerlach
observed two bands of
Ag atoms in their
experiment
 an angular momentum l
gives rise to 2l + 1
orientations, which is
equal to 2 only if
 l = ½ , contrary to the
conclusion that l must be
an integer
59

Spin
 Arose from the motion of the
electron about its own axis.  spin quantum number s (in
 Spin is an intrinsic angular place of l; like l, s is a non-
momentum of a fundamental negative number)
particle.  ms, the spin magnetic quantum
number, for the projection on
the z-axis.
 The spin of an electron about
its own axis does not have to  The magnitude of the spin
satisfy the same boundary angular momentum
conditions as those for a
particle circulating around a
central point Restricted to
 the quantum number for spin
angular momentum is subject to
different restrictions.
60

Electron
 only one value of s is allowed,
namely, s = ½ >> angular
momentum of magnitude
 intrinsic property of the

electron, like its rest mass and
its charge
 The spin may lie in 2s + 1 = 2
different orientations, ms = +
½ ( or ) and ms = + ½ (
or )
61

The properties of angular momentum
 the quantum numbers l and ml >> orbital angular
momentum (circulation in space)
 s and ms > spin angular momentum (intrinsic angular
momentum)
 J and mj > a combination of orbital and spin momenta

62
63
End of chapter 2
64

65

 the spherical harmonics for l = 0
to 4 and ml = 0,
 number of angular nodes (the
angles at which the wavefunction
passes through zero) increases as
the value of l increases.
 There are no angular
 nodes around the z-axis for
functions with ml = 0, which
corresponds to there
 being no component of orbital
angular momentum about that
axis
66

67

2.QM Theory Motion Rev16

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QUANTUM THEORY

Techniques and applications

 To calculate the properties of systems >>> solve the appropriate

QM Theory Dwi Hudiyanti  2016 4/5/2018

QM Theory Dwi Hudiyanti  2016 4/5/2018

QM Theory Dwi Hudiyanti  2016 4/5/2018

QM Theory Dwi Hudiyanti  2016 4/5/2018

 the value of C that

QM Theory Dwi Hudiyanti 2016 4/5/2018

 The energies and wavefunctions are labelled with

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

 quantum numbers n and n

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

although the wavefunctions are

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

 Transmission`probability for κL >> 1

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

The Schrödinger equation

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

 The energy separation

QM Theory Dwi Hudiyanti 2016 4/5/2018

 the smallest permitted  v cannot take negative

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

Hv(y) is a Hermite polynomial

QM Theory Dwi Hudiyanti 2016 4/5/2018

that the probability density

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

the mean displacement, x

the oscillator is equally likely to be found on

the mean square displacement, x2

corresponds to the classical amplitude of swing 39

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

not all the values of the angular

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

•ml, quantum number

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

 the angular momentum is quantized

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

 The wavefunction is therefore

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

QM Theory Dwi Hudiyanti 2016 4/5/2018

• If the angular momentum is