2.

2 The Photoelectric Effect

—Einstein’s Explanation (1905)
• Light energy is contained in discrete units, called Photons
• A photon (light quantum) gives all its energy to a single electron in the metal

Emax= hn-f h: Planck’s Constant

n: Frequency of light f: Work function of metal

• The energy of a photon

E = hn = hc/l

l: the wavelength fo the light

l=c/n

• Einstein won Nobel Prize in 1922 for his theory on Photoelectric Effect

Wave-particle duality of light!

 2.3 Atomic Structure and the Bohr Model

• Glowing solids and liquids (and even gases at high densities) emit a continuous
distribution of wavelengths—continuous spectrum.

• A low-pressure gas subject to electric charge gives a discrete line spectrum.

• Different elements give completely different line spectra—spectroscopy

(G. R. Kirchhoff, 1860, discovered rubidium and cesium)

For Hydrogen:

R = 109,678 cm-1 is the Rydberg constant Relationship among various series

—Ritz combination principle

Origin ?
The Bohr Model of Hydrogen Atom

1. The electron moves in certain stable, circular orbits about the proton (nucleus)
under the influence of the Coulomb force of the attractions.

2. The electron may shift to an orbit of higher or lower energy, thereby gaining or
losing energy equal to the difference in the energy levels (by absorption of emission
of a photon of energy hn).

3. The angular momentum pq of an electron in an orbit is quantized.

(2-10)

(2-17)

Where K = 4πe0
Figure 2—2
Some important lines in the emission spectrum of hydrogen.
Figure 2—3
Relationships among photon energies in the hydrogen spectrum.
Figure 2—4
Electron orbits and transitions in the Bohr model of the hydrogen atom.
Orbit spacing is not drawn to scale.
We also want to know the energy of the
electron
- the kinetic energy of the
electron is:

- the potential energy

is:

The total energy of the electron is the sum of the K.E. and
the P.E.

- substituting for rn
gives:

- rearranging, we obtain the energy of the electron in the nth

orbit as:
- substituting in values
gives:

- We are actually interested in the energy required for an electron to make a

transition between levels, that is from an initial level n1 to a new level n2,this is
given by:

- For a transition where the electron is initially in the 2nd orbit (n = 2):

The frequency
of absorbed
photon required
is:

Note:
 2.4 Quantum Mechanics
Bohr’s Principle of Complementarity: it is not possible to simultaneously describe
physical observables in terms of both particle and waves.

Physical Observables are those quantities such as position, momentum, velocity

and energy that can be experimentally measured.

Heisenberg Uncertainty Principle: if a measurement of position is made with precision

Dx, and a simultaneous measurement of momentum is made with precision Dpx, then the
product of the two uncertainties can never be smaller than the order of ħ, that is,

(2-18)

Other conjugate variables form uncertainty principle relations

(2-19)

The uncertainties expressed in above equations are intrinsic!

 Heisenberg’s Schrödinger’s
Matrix Mechanics º Wave Mechanics

The Schrödinger Wave Equation

- Each particle in a physical system is describable by a wave function Ψ that is a
function of position and time, that is Ψ(x,t).

- In its time-dependent form for a particle of total energy E moving in a

potential field V in one dimension:

(2-23)

in three dimensions

(2-24)
Classic Wave Equation

In this equation the wave function Y may be the amplitude of a water wave,
a guitar string vibration, or even the electric field E or magnetic field B

What is the nature of the wave function Y in Schrödinger’s equation?

Erwin with his psi can do

Calculations quite a few.
But one thing has not been seen
Just what does psi really mean?
—Walter Huckel

The Born Interpretation The probability that a particle with wave function Y will be found
in the infinitesimal interval dx about the point x, denoted by p(x)dx, is

Y* is the complex conjugate of Y

Basic Postulates of Quantum Mechanics

• |Y|2 or p(x) is called the probability density function. It is measurable and is just the
probability per unit length. P(x) must be normalized:

• The wave function Y(x,t) and its space derivative must be single-valued, finite, and
continuous.

• Each physical observable Q is related to a quantum mechanics operator Qop, from

which the expectation value áQñ can be calculated:
 Heisenberg’s Schrödinger’s
Matrix Mechanics º Wave Mechanics

The Schrödinger Wave Equation

- Each particle in a physical system is describable by a wave function Ψ that is a
function of position and time, that is Ψ(x,t).

- In its time-dependent form for a particle of total energy E moving in a

potential field V in one dimension:

(2-23)
Basic Postulates of Quantum Mechanics

• |Y|2 or p(x) is called the probability density function. It is measurable and is just the
probability per unit length. P(x) must be normalized:

• The wave function Y(x,t) and its space derivative must be single-valued, finite, and
continuous.

• Each physical observable Q is related to a quantum mechanics operator Qop, from

which the expectation value áQñ can be calculated:
 Let Y(x,t) be represented by y(x)f(t), the Schrödinger equation (2-23) can be
separated to obtain an equation containing f(t),

(2-26)

And the time-independent Schrodinger equation:

(2-27)

Total derivatives!

The Potential Well Problem

∞ ∞
V(x) V(x) = 0, 0<x<L

(2-28)
V(x) = ∞, x = 0, L
x
0 L
Inside the well we set V(x)=0 in Eq. (2-27)

(2-29)

Possible solution of Eq. (2-29)

Since outside the well y=0 and the interior wave must match the exterior wave at the walls
In order that y(x) be continuous everywhere,

Then, k must be some integral multiple of π/L

The total energy En for each value of integer n can be solved.

(2-33)
The nth wave function

The constant A is found by normalizing yn

(2-35)

• Energy is quantized; the possible energy

of En are called energy levels
• The integer n is called a quantum number
• The particular yn and corresponding En
describe the quantum state of the particle
• n=1 defines the ground state; its energy E1
is not zero
• Quantum states defined by n>1 are called
excited states
• f(t)=e-jwt by solving (2-26)®stationary state
Tunneling

Figure 2—6
Quantum mechanical tunneling:
(a) potential barrier of height V0
and thickness W; (b) probability
density for an electron with
energy E < V 0, indicating a non-
zero value of the wave function
beyond the barrier.

- Even for a particle with E<V0, quantum mechanics predicts that there is a finite
probability the particle will be found beyond the barrier. The mechanism by which
the particle “penetrates” the barrier is called quantum mechanical tunneling.

Zener effect Chap 5.4.

Device application Chap 10.1
Scanning Tunneling Microscope (STM)
2.5 Atomic Structure and The Periodic Table

The Hydrogen Atom

(2-45)

The spherical coordinate system

Quantum Numbers
n principle quantum number (주양자수) n=1, 2, 3, …
L orbital angular momentum quantum number (부양자수) l=0, 1, 2, 3,…, n-1
m magnetic quantum number (자기양자수) m= -l, -l+1, …0, 1, …, l-1, l
s spin quantum number (스핀양자수)

Every allowed energy state of the electron in a H atom is uniquely described by the
above four quantum numbers
 The Periodic Table—Quantum Mechanics Explanation

—The discovery of an empirical periodic table of elements, 1869, Demitri Mendeleev

—The elucidation of the underlying physical basis of the periodic table, late 1920s

Pauli Exclusion Principle: No two electrons in an atom may have the same set of quantum
numbers (n, l, m, s)

1. The electrons in an atom tend to occupy the lowest energy levels available to them
2. Only one electron can be in a state with a given (complete) set of quantum numbers
(Pauli exclusion principle)

—Some conventions:
Principle quantum number n=1, 2, 3, 4, … shells

The naming of l values l=0, 1, 2, 3, 4, …

s, p, d, f, g, … subshells
Electron state 3p6
Total electronic configuration of Si 1s22s22p63s23p2
The Schrödinger Wave Equation
- Each particle in a physical system is describable by a wave function Ψ that is a
function of position and time, that is Ψ(x,t).

- In its time-dependent form for a particle of total energy E moving in a

potential field V in one dimension:

(2-23)

- Let Y(x,t) be represented by y(x)f(t), the Schrödinger equation (2-23) can be

separated to obtain the time-dependent Schrödinger equation:

(2-26)

- And the time-independent Schrödinger equation:

(2-27)

Total derivatives!
The Potential Well Problem

∞ ∞
V(x) V(x) = 0, 0<x<L

V(x) = ∞, x = 0, L
x
0 L

- Inside the well we set V(x)=0 in Eq. (2-27)

- Solving (and normalizing) gives the nth wave function:

- The total energy En for each value of integer n can be solved.

2.5 Atomic Structure and The Periodic Table

The Hydrogen Atom

(2-45)

The spherical coordinate system

Quantum Numbers
n principle quantum number n=1, 2, 3, …
l orbital angular momentum quantum number l=0, 1, 2, 3,…, n-1
m magnetic quantum number m= -l, -l+1, …0, 1, …, l-1, l
s spin quantum number

Every allowed energy state of the electron in a H atom is uniquely described by the
above four quantum numbers
 The Periodic Table—Quantum Mechanics Explanation

—The discovery of an empirical periodic table of elements, 1869, Demitri Mendeleev

—The elucidation of the underlying physical basis of the periodic table, late 1920s

Pauli Exclusion Principle: No two electrons in an interacting system may have the
same set of quantum numbers (n, l, m, s)

1. The electrons in an atom tend to occupy the lowest energy levels available to them
2. Only one electron can be in a state with a given (complete) set of quantum numbers
(Pauli exclusion principle)

—Some conventions:
Principle quantum number n=1, 2, 3, 4, … shells
sharp
The naming of l values l=0, 1, 2, 3, 4, … subshells principal
s, p, d, f, g, … diffuse
fundamental
Electron state 3p6
6 electrons in the 3p alphabetical
(n=3) (l=1) subshell

Total electronic configuration of Si 1s22s22p63s23p2

Total electronic configuration of Si 1s22s22p63s23p2
 Total electronic configuration of Si
1s22s22p63s23p2 = [Ne]3s23p2=[Ne]sp3

• Closed p shells® He, Ne, Ar,…

• valence electrons® Electrons
outside an inert core
• valence® determines the
chemical activity
• Si and Ge have similar
electronic structure and properties
Figure 2—8
Electronic structure and energy levels in a Si atom: (a) The orbital model of a Si atom
showing the 10 core electrons (n = 1 and 2), and the 4 valence electrons (n = 3).
Figure 2—8
Electronic structure and energy levels in a Si atom: (b) energy levels in the coulombic
potential of the nucleus are also shown schematically.
Figure 2—9
Orbitals in a Si atom: The spherically symmetric “ s” type wave functions
or orbitals are positive everywhere, while the three mutually perpendicular
“p” type orbitals ( p x , p y , p z ) are dumbbell shaped and have a positive
lobe and a negative lobe. The four sp 3 “hybridized” orbitals, only one of
which is shown here, point symmetrically in space and lead to the
diamond lattice in Si.