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Wave-particle Duality

Wave-particle Duality 1
This generic diagram can be used to represent waves of different types,
including photons:

In general the wave amplitude varies with both distance and time.

The peaks occur at the same place in stationary waves (otherwise the
peaks move in some direction), but in all waves the amplitude varies with

Wave-particle Duality 2
The Energy and Momentum of Light Wave-Particle Duality
The electric field amplitude of a light wave traveling through space is given by:

E ( x, t ) = E0 cos (t kx )

where t = time; x = position; and = radian frequency. In some books, you

will find the expression written in terms of wavelengths.

2 c 2
E ( x, t ) = E0 cos t x

Here, is of course the wavelength. The first term in parentheses shows the
time-dependence of the amplitude, whereas the second term deals with the
distance dependence.
Comparing the two equations, we note that: = 2c/ = 2 and k = 2/ .
(For interest, the ratio /k = = c, the velocity of light).

Wave-particle Duality 3
This equation conveys two important pieces of information about the wave-
particle duality of photons. Thus:
Energy = ( = h )
Momentum =
Thus, not only do photons have a wavelength, but they also behave like
particles, having definite amounts of energy and momentum. The quantity k,
which relates to photon linear momentum, is a measure of the number of
wavelengths per unit distance (k = 2/). k is strictly a vector quantity, which is
important in optics, but we often deal just with its magnitude.

All matter has both wave-like and particle-like properties, although the
wave-like properties are only clearly revealed for particles with very small

Wave-particle Duality 4
Several conservation rules in physics also apply to small particles, including

Energy (assuming no mass-energy conversion, which is OK for most

spectroscopic purposes) e.g., the condition of resonance.

Linear momentum Compton scattering (X-ray photon + electron),

nonlinear optics (lasers; photon-photon interactions)

Angular momentum fundamental conservation rule in spectroscopy a

photon carries 1 unit (h/2) of angular momentum governs light-induced
changes in the angular momentum quantum numbers of atoms and molecules.
Very strong selection rule, e.g., controlling the form of microwave and NMR
spectra, as well as in IR and electronic spectroscopy, for example.
Wave-particle Duality 5
1. Conservation of energy:
2. Conservation of angular
momentum determines the
= = = 100 position and spacing of the
resonances due to rotation. (
= 1)

Phys Chem 1 - Introduction 6

Some examples of spin in fundamental particles:

1. Fermi-Dirac particles spin = n+, where n=0,1,2

Examples: electrons, protons, neutrons, many atomic nuclei (e.g., 1H, 3He, 13C)

2. Bose-Einstein particles spin = 0,1,2,3

Examples: photons, and many atomic nuclei (e.g., 2H, 4He, 14N, 12C, 16O)

Other relevant examples of angular momentum

1. Orbital angular momentum in hydrogen (e.g., p, d, f orbitals but not s)

2. Rotational angular momentum in many molecules (e.g., CO2 bend and stretch,

3. Vibrational angular momentum in many molecules (e.g., CO2 bend, CH4 -


Wave-particle Duality 7
What are some typical wave-like properties?

Diffraction of electrons, neutrons and helium atoms

- the interaction of a wave with a regular array of scattering objects
- a diffraction pattern is actually a special case of the property of

Interference the more general property, of which diffraction is an

example - atomic wavefunctions interfere both constructively and destructively
when two atoms approach one another.
- Photons undergo constructive interference (spatial
coherence) to form laser beams, and in particular to form ultrashort pulses
(spatial and temporal coherence).

Wave-particle Duality 8
Lecture demonstration of diffraction of a laser pointer from a diffraction grating

Laser diffraction
pattern on screen 3


n=0 (zero-order diffraction n=0

spot) is the same as the
undeflected beam
Transmission grating with linear rulings
spaced close to the wavelength of light.
500 rulings per mm (rulings spaced
0.001/500 = 2.0 x 10-6 m). Laser spot overlaps
Laser ~1000 rulings.

Wave-particle Duality 9
Using the data from above and the appropriate form of the Bragg equation, can
calculate the divergence angles, , for the different diffraction spots:
Outgoing diffracted beam
comprises ~1000 diffracted

Path difference between

Incoming laser overlaps adjacent rays = d sin = n
possibly 1000 rulings on d
the grating

Beam deflected by angle

If the grating has 500 rulings per

mm, the deflection angle for n=1,
with a 532 nm laser, is ~0.27
radians (~ 15.40)
Wave-particle Duality 10
Laser diffraction
pattern on screen

Transmission grating with square array of

points spaced close to the wavelength of
light. Laser spot overlaps ~1000 points.


Wave-particle Duality 11
de Broglie's Hypothesis

The de Broglie relationship combined the particle and wave properties of any
particle into a simple equation:


Here, the quantity p is the linear momentum, which would be the same as
the product mv" for a particle having a finite "rest" mass. This does not
include photons, for which we need to use p = hk/2 (or k).

The de Broglie relationship is perfectly general, although only objects on the

size of small molecules or small atoms usually can manifest both wave and
particle properties.

Wave-particle Duality 12
Example, calculate the de Broglie wavelength for an electron having a kinetic energy of
1 eV.
Recall that the energy equivalent of 1 eV is 1.602 x 10-19 Joules, so that:

p2 h2
= = 1 eV = 1.602 1019 Joule
2me 2me 2


h2 (6.626 1034 ) 2 18
= = 31 19
= 1.4 10 m 1.2 nm
2me Ek 2 9.1110 1.602 10

For a more massive particle, the de Broglie wavelength at the same kinetic
energy decreases with the square root of the mass.

The heavier particle almost always has larger physical dimensions, and quickly
the de Broglie wavelength (and wavelike behavior) becomes less significant.

Wave-particle Duality 13
Some Other Examples:

Particle (nm)

Electron at 300 K 6.1

100-volt electron. 0.12

He atom at 300 K 0.079

Xe atom at 300 K 0.012

Wave-particle Duality 14
The calculation for the helium atom at 300 K is as follows:

8k BT 8mk BT h Here, the bars imply averages - one

p = mu = m = = could also use brackets. (p. 1114)
h 6.626 1034
= = = 7.92 1011 m
8mk BT 8 4 1.66054 1027 1.381 1023 300

For a Maxwell-Boltzmann distribution of molecular velocities one may expect a

wide range of de Broglie wavelengths. In experimental applications, such as
helium or neutron diffraction, it is common to use a mechanical velocity
selector, for example, using a pair of rotating-sector beam choppers. This
narrows the range of de Broglie wavelengths from a thermal source of atoms or

Wave-particle Duality 15
M&S Figure 27.2,
showing the Maxwell-
Boltzmann distribution
of molecular speeds for
different temperatures.

(Details covered in Chem

222; See M&S Ch 27.)

Wave-particle Duality 16
Gas molecule velocity selector

Molecules emerging at a variety of

speeds from the source travel into
the spiral slot on the rotating drum.
Only molecules traveling in a
narrow range of velocities will
travel through the sequence of slots
without undergoing collisions with
the vanes.

This would also give a narrow

range of de Broglie wavelengths,
such as needed in a diffraction

See M&S Chapter 27, Figure 27.9 and Chem 222

Wave-particle Duality 17
An example of the use of a beam of D2
molecules as a diffraction probe of a
metal surface under high vacuum

Wave-particle Duality 18
The deBroglie wavelength of a particle depends on the local environment,
because the momentum is usually variable.
Consider that the total energy, E, of a particle can be expressed by:
1 2 p2
E = KE + PE = mv + V = +V
2 2m
From this, we can write an expression for the momentum of the particle:

p = 2 m( E V ) (See Ch. 3)

Then, applying the deBroglie expression, we find for the wavelength:

2 m( E V )
Thus, as the potential energy increases, the deBroglie wavelength of the
particle increases, and the momentum decreases. Note that the difference
between E and V is the kinetic energy, which also decreases as V increases.

Wave-particle Duality 19
A good example of a variable potential energy is the harmonic oscillator, where
we can deduce that, if the total energy is constant, both the potential and kinetic
energy terms vary with time.

In the case that E<V, we need quantum mechanics to explain the behavior of the
particle. (See tunneling discussion later in connection with Chapter 4).

Wave-particle Duality 20
The Heisenberg uncertainty principle
Closely related to the deBroglie relationship is the Heisenberg uncertainty
principle. This is expressed mathematically as:

If we specify the momentum, then the de Broglie formula tells us that there is a
definite wavelength representing the particles.

Wave-like behavior of a particle with a definite momentum

(1-eV electron)

Amplitude (arbitrary


0 1.2 2.4 3.6 4.8 6 7.2 8.4 9.6 10.8 12
Distance (nm)

Wave-particle Duality 21
We ask the question: Where is the particle?

The best we can do is to say that the probability of locating the particle is
proportional to the square of the amplitude of the function: (One of the
postulates of Quamtum Mechanics see later)

Probability of locating a 1-eV electron in space






0 1.2 2.4 3.6 4.8 6 7.2 8.4 9.6 10.8 12

Where is it? It could be anywhere under the blue sine wave.
Why? We specified an exact momentum with no uncertainty, leaving us with
infinite uncertainty of the position. (Actually this is not quite infinite uncertainty,
since we know the particle cannot be at the nodes of the wave function).
Wave-particle Duality 22
Schematic representation of the DeBroglie

and Heisenberg principles

- more details will come later

Wave-particle Duality 23
A single wave provides no information
A single wave provides no information
about the particle location except for local
about the particle location except for local
maxima and minima
maxima and minima

Wave amplitude

Amplitude squared
0.5 0.8
0 0.6
-0.5 0.4

Left-hand graph shows a single Right-hand graph shows the

cosine wave consistent with a square of the amplitude of the
definite value of p and wave, and describes the spatial
probability distribution. For a
given there is a very large
uncertainty in the position.

Wave-particle Duality 24
Now, we overlap (arbitrarily) seven different waves of different wavelength, to
simulate some uncertainty in the actual wavelength and momentum. They are
chosen for this demonstration to overlap exactly in the middle, whereas they fall
out of phase toward the edges. This generates a wave packet. There are many
ways to pick the component waves, including both wavelength and amplitude.





0 50 100 150 200

Wave-particle Duality 25
Adding 7 different waves together localizes Adding 7 different waves together localizes
the particle - here amplitude the particle - here amplitude squared


Ampliutude squared
1 1

0.5 0.8
0 0.6
-0.5 0.4
0 50 100 150 200
0 50 100 150 200

Left-hand graph shows the result of Right-hand graph shows the

adding the 7 waves together to square of the resulting amplitude,
create a wave packet. The waves and describes the spatial
have different wavelengths, so that probability distribution. The
we can't stipulate the wavelength or wave packet describes the
momentum of the particle exactly. location of the particle much
Now we have built in an uncertainty better - there is a much smaller
to the momentum. uncertainty in the position.

Wave-particle Duality 26
Therefore, the model above has defined both p and x, which are the
uncertainties in momentum and position, respectively. If we were to quantify
these values, we could see how this would be consistent with the Heisenberg
Uncertainty relationship.

However, an important question remains as to how exactly we define x and


Wave-particle Duality 27
Mathematical representation of uncertainty

In Math Chapter B, the book introduces the concept of variance, 2, which

allows us to calculate the uncertainty in terms of the standard deviation, .
Thus, if we have a functional form for some quantity, we can also calculate an
uncertainty, which can have wide implications in experiment and theory.

(x x )
x2 =
Proof is in Math Chapter B
or more commonly: - not needed in this course.
x2 = x 2 x

This concept is important in a number of ways in this course, to handle

theoretical uncertainties. It is also important experimentally, in error
analysis. We shall use this type of idea in several places later on.

Wave-particle Duality 28
Lets put some numbers together for the above example of a wave packet
I picked 7 different wavelengths of arbitrary values, 17, 18, 19, 20, 21, 22 and 23
distance units. The actual units dont matter as they will cancel.
Using the deBroglie relationship, p=h/, we can specify that the equivalent
momenta, p, are: 1/17, 1/18 etc units of h the Planck constant.
A simple calculation shows that this gives a standard deviation, p, of 0.0055 h,
which is equivalent to the spectral distribution actually used.

Now, the combination of these waves gives us a wave packet, for which we can
estimate an uncertainty in the position. (Review Slide 25). In these arbitrary units,
the fwhm of the distribution is near 50 units, which we take to be close to the value
of x, the uncertainty in position.

Multiplying the two quantities together, we get: p x ~ 0.28 h.

(Note: h/4 ~ 0.08h). Wave-particle Duality 29
This admittedly crude calculation tells us that the product of the uncertainties is
less than the value of h, but likely greater than h/4.
This conclusion is consistent with the spirit of the Heisenberg relation. More
detailed examples later will reinforce the idea.

Bottom line:
When constructing a wave packet to define more clearly the location of a
particle, we need to include a greater number of distinct wavelengths. This
improvement in positional precision is at the expense of precision in our
knowledge of the wavelength and hence momentum.
The Heisenberg principle defines the limits on the simultaneous precision of
these two types of measurement.

Wave-particle Duality 30
Suppose we take an electron confined to a region approximately 1.2 nm wide
(i.e., the dimensions of a large molecule or a small nanoparticle)


0.8 This figure shows the type of


0.6 function that may be used to

describe a confined wave.

-1.5 -1 -0.5 0 0.5 1 1.5
See also Example 1-11
Distance (nm)

What is the uncertainty in the momentum?

Take x = 1.2 nm.
= = 4.39 10
What is the uncertainty in the velocity?

= = 4.82 10$
Wave-particle Duality 31
The velocity uncertainty seems large. Would that not also imply that the electron
velocity is large? Yes. Lets take the example of an electron confined to a classical
Bohr orbit (n=1) in a hydrogen atom. Kinetic energy is numerically equal to the
value of the Rydberg constant. (In fact, quantum mechanics stipulates that we
cannot know the exact KE, and the best we can do is to calculate an average value)
1 2
mv = 2.178 1018 Joule
2.178 1018 2
v= 31
= 2.19 106 m s-1
This observation means that the electron is traveling close to 1% of the velocity of
light, even in the H atom. The energy of the electron closest to nucleus in
different atoms (Moseley) scales approximately with Z2, raising the interesting
possibility that the electrons in heavy atoms could have velocities approaching
the velocity of light. In this domain, the mass of the electron is no longer
constant, increasing as the velocity approaches that of light. This phenomenon is
a consequence of the theory of relativity, and the needed corrections to the
various formulas are termed relativistic. Such corrections are needed to explain
the properties of heavier elements, such as Hg and Au. 32