Chemistry 5

Chapter-9
Electrons in Atoms
Part-2

28 October 2002
 Wave-Particle Duality
ƒ If light energy has particle-like properties, does matter
have wave-like properties? Rem: photoelectric effect where individual
photons must have energy >threshold to observe
electron ejected from metal surface.
ƒ de Broglie: Small particles of matter may display wavelike
properties!
• photon: E(photon) = hν and c = νλ
• matter: E = mc2
hν = mc2
hν/c = mc
But c = νλ, and mc is momentum, p
h/λ = p
Now for particle of mass, m, and
velocity, u:
h h
λ= = de Broglie wavelength
mu p
 Does electron exhibit wavelike properties?
ƒ G.P. Thomson passed an electron beam through a sheet of
gold foil and observed intensity vs. deflection angle:

electron gun

gold foil

“Diffraction Pattern”
ƒ Key Observations & Implications:
• As detector is moved the intensity of transmitted electron varies
(similar behavior is observed when X-ray source is used)
• These results imply that the electrons (X-rays) interfere when they
pass through the gold film. This interference phenomena is called
diffraction and is due to the wavelike properties of electrons.
Viewing Atoms and Electrons: Tunneling Microscope
sample
transfer

preparation
ion sample ion

sample
pump storage
I pump

optical table
Vb

air legs UHV

Au

vacuum
dewar can
Ground LHe

STM 9-11 T
microscope Solenoid
 Electrons Waves & Interference!

-0.447 eV

-0.414 eV

-0.384 eV

(dI/dV)/(I/V) (a.u.)
-0.293 eV

0.171 eV

El
0.231 eV
Teikx
Ek
Reikx Ej
Ei 0.311 eV
eikx
x 0
0.368 eV

0.415 eV
Au

ψ(k,x)=e-ikx+|R|e-i(kx+δ) 0.0 1.0 2.0 3.0

Distance (nm)
ρ(k,x)= |ψ(k,x)|2=1+|R|2+2|R|cos(2kx+δ)
Ouyang, Huang, and Lieber, Science
 Wave-Particle Duality: Summary
ƒ Mass-Wavelength:
• MASS INCREASES Æ Wavelength gets shorter
• MASS DECREASES Æ Wavelength gets longer
ƒ How important is this?
• What are the “de Broglie wavelengths” of a 0.10 kg baseball
moving at 35 m/s and an electron moving at 1.0 x 107 m/s?
h h = 6.626 x 10-34 J s
λ=
mv 1J = kg m2 s-2

Baseball Electron
− 34 6.626 × 10− 34 Js
6.626 × 10 Js λ=
λ= (9.11 × 10− 31 kg )(1 × 107 m / s )
(0.10kg )( 35m / s )
= 1.9 x 10-34 m = 7.3 x 10-11 m
More massive particle– baseball– has immeasurably small wavelength!
 The Uncertainty Principle
ƒ Laws of classical physics enable precise predictions of
position and velocity………however, you cannot pin an
electron down!
ƒ Heisenberg postulated the following:
• ∆x is the uncertainty in the particle’s position
• ∆p is the uncertainty in the particle’s momentum
then: h Effect of mass included in momentum:
∆x∆p ≥
4π ∆p = m ∆v
ƒ Implications?
• there is a fuzziness intrinsic to all small things
• or put another way– for particle like an electron
we can never know both position and velocity to any
meaningful precision at the same time!
 The Uncertainty Principle: Examples
ƒ What is the uncertainty in velocity for baseball and
hydrogen atom, if we assume that position is known to 1%?
ƒ Baseball: 1
Size ~ 0.5 m Î ∆x = × 0.05m = 5 × 10−4 m
100
h 1 1
∆v ≥ × × = 1 x 10-30 m/s
4π m ∆x
Can play baseball without worrying about Heisenberg’s Uncertainty Principle!

ƒ Hydrogen Atom:
Assume we estimate position to 1% of radius of H-atom, then
1
∆x = × 0.05nm = 5 × 10− 4 nm = 5 × 10−13 m
100
h 1 1
∆v ≥ × × ∆v = 1.15 × 108 m / s
4π m ∆x
The uncertainty in the velocity is enormous!!
 Quantum Mechanics
ƒ We cannot know precisely where electrons are!
ƒ This means we cannot describe the electron as
following a known path such as a circular orbit.
ƒ What about Bohr Model?
Bohr’s model is therefore fundamentally incorrect
in its description of how the electron behaves.
ƒ Wave Description– Look at demonstration first:
• Waves have amplitude that depends on position
• Wavefunctions can have different shapes– defined by nodes–
between boundaries
• Can identify well-defined/repeatable nodal structures
• The number of nodes depends on energy added to system
 Was Bohr upset with Heisenberg?
BOHR

HEISENBERG

AND THIS IS??

Niels Bohr and Werner Heisenberg dining (1934)
 Wave Functions
ƒ Schrodinger equation:
• Schrodinger showed that functions– now called wave functions–
describing a quantum system can be obtained by solving a wave equation.
• These wave functions are called orbitals
ƒ Description of Orbital (vs. Bohr’s orbits):
• ψ(r, θ, φ) = R(r)Y(θ, φ)
• radial wave function– R(r) – depends only on distance from nucleus
• angular wave function– Y(θ, φ)– depends on
angular part of polar coordinates

Each wave function has three numbers,

called quantum numbers that define the
general functional form of R(r) and
Y(θ, φ)– and hence an orbital shape.
 Quantum Numbers (beyond Bohr model)
ƒ Quantum Numbers (are part of orbital/wave function description)
• principle, n -- positive, nonzero integer values n = 1, 2, 3, …

• orbital angular momentum, l -- zero or positive integer with values l =

1, 2, 3, …, n-1
• magnetic, ml -- negative or positive integer, including zero with values
ml = 0, ±1, ±2, ±3, …±l

ƒ Principle Shells and Subshells

• Orbitals with the same value of n, are in same principle electronic shell
• Orbitals with the same values of n and l, are in same subshell
s orbitals p orbitals d orbitals
l=0 l=1 l=2
ml = 0 ml = 0, ±1 ml = 0, ±1, ±2
one s orbital in three p orbitals five d orbitals in
s subshell in p subshell d subshell
 Wave functions, orbitals & probabilities
ƒ Wave functions and probabilities:
• Wave function itself does not have physical significance, although sign (+/-) tells
us about phase and is important for describing chemical bonds.
• The square of the wavefunction, ψ2, has physical meaning as electron probability
density (or charge density)and is used to describe shape…….lets examine this
point!
ƒ s-orbitals

n-1 radial nodes