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l15 chapt9-2 web

l15 chapt9-2 web

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Chemistry 5

Chapter-9 Electrons in Atoms Part-2 28 October 2002

Wave-Particle Duality
If light energy has particle-like properties, does matter have wave-like properties? Rem: photoelectric effect where individual de Broglie: Small particles of matter may display wavelike properties!
• • photon: matter: E(photon) = hν and c = νλ 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:
photons must have energy >threshold to observe electron ejected from metal surface.

h h λ= = mu p

de Broglie wavelength

Does electron exhibit wavelike properties?
G.P. Thomson passed an electron beam through a sheet of gold foil and observed intensity vs. deflection angle: θ
electron gun gold foil

Key Observations & Implications:

“Diffraction Pattern”

• 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

ion pump

sample preparation

sample storage

I

ion pump

optical table air legs UHV

Vb

Au
vacuum can
LHe

dewar

Ground
STM microscope

9-11 T 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 0.231 eV 0.311 eV 0.368 eV 0.415 eV

El Reikx x eikx 0 Ek Ej Ei

Teikx

Au

ψ(k,x)=e-ikx+|R|e-i(kx+δ) ρ(k,x)= |ψ(k,x)|2=1+|R|2+2|R|cos(2kx+δ)

0.0

1.0

2.0 Distance (nm)

3.0

Ouyang, Huang, and Lieber, Science

Wave-Particle Duality: Summary
Mass-Wavelength:
• MASS INCREASES • MASS DECREASES Wavelength gets shorter Wavelength gets longer

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 λ= mv
Baseball

h = 6.626 x 10-34 J s 1J = kg m2 s-2 Electron

6.626 × 10 Js λ= (0.10kg )( 35m / s )
= 1.9 x 10-34 m

− 34

6.626 × 10− 34 Js λ= (9.11 × 10− 31 kg )(1 × 107 m / s )

= 7.3 x 10-11 m

More massive particle– baseball– has immeasurably small wavelength!

The Uncertainty Principle
Laws of classical physics enable precise predictions of position and velocity………however, you cannot pin an electron down! Heisenberg postulated the following:
• • ∆x is the uncertainty in the particle’s position ∆p is the uncertainty in the particle’s momentum

then:

h ∆x∆p ≥ 4π

Effect of mass included in momentum:

∆p = m ∆v

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
What is the uncertainty in velocity for baseball and hydrogen atom, if we assume that position is known to 1%? Baseball:
Size ~ 0.5 m

∆x =

1 × 0.05m = 5 × 10−4 m 100

h 1 1 ∆v ≥ × × 4π m ∆x
Hydrogen Atom:

= 1 x 10-30 m/s

Can play baseball without worrying about Heisenberg’s Uncertainty Principle!
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
We cannot know precisely where electrons are! This means we cannot describe the electron as following a known path such as a circular orbit. What about Bohr Model? Bohr’s model is therefore fundamentally incorrect in its description of how the electron behaves. 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
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

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)
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

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
l=0 ml = 0 one s orbital in s subshell

p orbitals
l=1 ml = 0, ±1 three p orbitals in p subshell

d orbitals
l=2 ml = 0, ±1, ±2 five d orbitals in d subshell

Wave functions, orbitals & probabilities
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!

s-orbitals

n-1 radial nodes

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