ATOM Models of Atom

Atomic Theory of Matter Dalton’s Model of atom

- Experiments in the 18th and 19th centuries led
to an organized atomic theory by John
Dalton in the early 1800s, which explained
several laws known at that time:
o The law of constant composition
o The law of conservation of mass
o The law of multiple proportion
The law of constant composition (Joseph Proust)

- Known as the law of definite proportions. J.J Thompson’s Model of Atom

- The elemental composition of a pure substance
never varies.
- In a given compound, the relative numbers and
kinds of atoms are constant
- Basis of Dalton’s Postulate #4

The law of conservation of mass (Antoine Laurent

Lavoisier)

- The total mass of substances present at
the end of a chemical process is the same
as the mass of substances present before
the process took place.
- Basis of Dalton’s Postulate #3
- Can’t create matter in a chemical reaction!
Rutherford’s Model of Atom
The law of multiple proportion
- If two elements A and B combine to form
more than one compound, the masses of B
that can combine with a given mass of A are
in the ratio of small whole numbers.
- pictures a sphere of positive charge. The
negatively charged electrons were spread
evenly among the positive charge.
- Atoms were neutral
- The number of electrons within an element
can vary.
- Most of the mass of the atom and its positive
charge is in the nucleus of the atom
- Electrons are orbiting the nucleus
Rutherford’s Model of Atom
- Rutherford predicted (in 1920) that another kind
of particle must be present in the nucleus along
with the proton
E. Goldstein’s Theory
- discovered the proton in cells. He made this
discovery by using a hydrogen gas-filled
tube, which was similar to Thomson's tube.
These positively charge particles were called
protons, and their mass is 1.837 times the
mass of the electron.
- mass
Bohr’s Model of Atom
- Problems with Rutherford's model: for
example, it could not explain the very
interesting observation that atoms only emit
light at certain wavelengths or frequencies
- Niels Bohr solved this problem by proposing
that the electrons could only orbit the nucleus
in certain special orbits at different energy
levels around the nucleus.
Atomic Structure
Electron
Mid 1800’s – scientists studied electrical discharge
through partially evacuated tubes.
- JJ Thomson proposed in 1897 that Cathode
Rays were particles (negatively charged) that
we now know are electrons.
- Thomson measured the charge/mass ratio of
the electron to be 1.76x108
coulombs/gram (C/g).
- Once the charge/mass ratio of the electron
was known, determination of either the
charge or the mass of an electron would yield
the other.
- Mass of an e-, (1.6010-19 C) / (1.76108
C/g) = 9.11 10-28 g.
Radioactivity
- The spontaneous emission of radiation by an
atom.
- First observed by Henri Becquerel. Also
studied by Marie (1867-1934) and Pierre
Curie (1857-1906). Discovered Po and Ra.
Suggested that atoms of certain substances
can disintegrate
Three types of radiation were discovered by
Ernest Rutherford:
- α particles positively charged (+2), large
mass
- β particles negatively charged (-1), small
- γ rays no charge, no mass
Nucleus
Discovery of Nucleus
- Ernest Rutherford shot α particles at a thin
sheet of gold foil and observed the pattern of
scatter of the particles.
Nuclear Atom
- Since some particles were deflected at large
angles. Thomson’s model could not be
correct.
- Rutherford’s nuclear model of the atom: all
of the positive charge and most of the
mass is concentrated at the center – the
nucleus.
- Electrons occupy the rest of the space
(volume) of the atom.
 - Neutrons were discovered by James
Chadwick in 1932.

Electronic Configuration - Total electrons = atomic number

- Fill energy levels with electrons until you run
- Electrons exist in different energy levels
out
(previously described as “shells”)
- The energy levels correspond to the
horizontal rows on the periodic table Aufbau (Building-Up) Principle - Electrons are
placed into the atomic orbitals filling from bottom to
Orbitals - are areas within shells where the electrons
top (like water in a jug) from lowest to highest energy
are Located
(i.e. most stable to least stable). The Aufbau
- These orbitals may have different shapes principle means fill the orbitals from bottom to
- There may be different numbers of orbitals top.
within a shell
Hund's rule of Maximum Multiplicity - If orbitals of
- The electron is somewhere in the orbital, but
equal energy (i.e. degenerate orbitals) are being
we can’t know exactly where it is or how fast
filled, the electrons are placed into each orbital in the
it is moving
degenerate set before they are spin paired with
o Heisenberg’s Uncertainty Principle
another electron in the same orbital. Hund's rule
- Each orbital can hold two electrons (Pauli
requires single occupancy before pairing.
Exclusion Principle)
Pauli Exclusion Principle - No two electrons in a
Types of Orbitals (Subshells)
atom can have an identical set of four quantum
- S orbitals – 1 orbital per shell – holds 2 numbers. This means an orbital can hold a
electrons total maximum of two electrons, and then the electrons
- P orbitals – 3 orbitals per shell – holds 6 must have opposite spins, +1/2 and -1/2.
electrons total
- D orbitals – 5 orbitals per shell – holds 10
electrons total
- F orbitals – 7 orbitals per shell – holds 14
electrons total
Electronic Configuration - is the arrangement of
electrons around the nucleus of an atom based on
their energy level.
- Low Energy to High Energy (# of electrons)
o 1s (2)
o 2s (2)
o 2p (6)
o 3s (2)
o 3p (6)
o 4s (2)
o 3d (10)
o 4 p (6)
o 5s (2)
Quantum Mechanics
- is used to explain microscopic phenomena
such as photon-atom scattering and flow of
the electrons in a semiconductor.
- is a collection of postulates based on a huge
number of experimental observations.
- The differences between the classical and
quantum mechanics can be understood by
examining both
Waves as Particles
o The classical point of view
o The quantum point of view
Quantum Mechanics in a Classical POV
- In Newtonian mechanics, the laws are written
in terms of PARTICLE TRAJECTORIES.
PARTICLE - is an indivisible mass point object
that has a variety of properties that can be
measured, which we call observables. The
observables specify the state of the particle
(position and momentum).
SYSTEM - is a collection of particles, which
interact among themselves via internal forces,
and can also interact with the outside world via
external forces. The STATE OF A SYSTEM is a
collection of the states of the particles that
Black Body Radiation
comprise the system.
Quantum Mechanics in a Quantum POV
- can act as both particles and waves WAVE-
PARTICLE DUALITY
- Quantum state is a conglomeration of several
possible outcomes of measurement of
physical properties ➔ Quantum mechanics
uses the language of PROBABILITY theory
(random chance)
- An observer cannot observe a microscopic
system without altering some of its
properties. Neither one can predict how the
state of the system will change.
Heisenberg Uncertainty Principle
Black Body Radiation Example
- One cannot unambiguously specify the
values of particle's position and its
momentum for a microscopic particle, i.e.
1ℎ
∆𝑥(𝑡0 )(∆𝑝(𝑡0 )) ≥ 𝜋 bouncing around inside the box with a
22
- Position and momentum are, therefore,
considered as incompatible variables
Correspondence Principles
- When Quantum physics is applied to
macroscopic systems, it must reduce to the
classical physics.
Particle-Wave Duality
- The behavior of a "microscopic" particle is
very different from that of a classical particle
o in some experiments it resembles
the behavior of a classical wave (not
localized in space)
o in other experiments it behaves as a
classical particle (localized in space)
- Max Plank work on black-body radiation
assumed that the molecules of the cavity
walls, described using a simple oscillator
model, can only exchange energy in
quantized units.
- 1905 Einstein proposed that the energy in
an electromagnetic field is not spread out
over a spherical wavefront, but instead is
localized in individual clumbs – quanta.
- Each quantum of frequency n travels
through space with speed of light, carrying
a discrete amount of energy and momentum
=photon => used to explain the photoelectric
effect, later to be confirmed by the x-ray
experiments of Compton.
- Known since centuries that when a material
is heated, it radiates heat and its color
depends on its temperature
- A material is constantly exchanging heat with
its surrounding (to remain at a constant
temperature):
o It absorbs and emits radiations
o Problem: it can reflect incoming
radiations, which makes a theoretical
description more difficult
(depends on the environment)
- A blackbody is a perfect absorber:
o Incoming radiations is totally
absorbed and none is reflected
- Blackbody - a cavity, such as a metal box
with a small hole drilled into it.
- Incoming radiations entering the hole keep
negligible change of escaping again through
the hole => Absorbed.
- The hole is the perfect absorber, e.g. the
blackbody Radiation emission does not
depend on the material the box is made of
=> Universal in nature

Particles as Waves
- Double-slit experiment, in which instead of
using a light source, one uses the electron
gun. The electrons are diffracted by the
slit and then interfere in the region
between the diaphragm and the detector.
- Aharonov-Bohm effect
Wien’s Displacement Law
- The intensity (λ, T) is the total power radiated
per unit area per unit wavelength at a given
temperature
- Wien’s displacement law states that the
maximum of the distribution shifts to smaller
wavelengths as the temperature increases.
Stefan-Boltzmann Law
- The total power radiated increases with the
temperature
𝑥 of the light.
𝑅(𝑇) = ∫ 𝐼(λ, 𝑇)dλ = ɛσ𝑇 −4
0
- 𝛔= 5.6705X10-8 W/m2K4
- Emissivity – simply the ratio of the emissive
power of an object to that of an ideal
blackbody
Rayleigh-Jeans Formula
2𝜋𝑐𝑘𝑇
𝐼(𝜆, 𝑇) =
𝜆4
Classical Physics
Emission Spectrum - a superposition of
electromagnetic waves of different frequencies
- Frequencies allowed: standing waves inside
the cavity
Equipartition of the energy:
- Every standing wave carries kT of energy
- Flaw: when l → 0, the number of standing
waves ↑, leading to E → ∞
Max Planck
- Planck assumed that the radiation in the
cavity was emitted and absorbed by some
sort of oscillators contained in the walls
- Planck’s radiation law
2𝜋𝑐 2 ℎ 1
𝐼(𝜆, 𝑇) = 5 𝑘𝑐
𝜆
𝑒 𝜆𝑘𝑇 − 1
Planck’s Modification of the Classical theory
- Oscillators can only have certain discrete
energies determined by En= nhv where n is
an integer, v = frequency and h = planck’s
constant
- h = 6.626 x 10-34 Js
- oscillators can absorb or emit energy in
discrete multiplies of fundamental quantum of
energy given by
- △ 𝐸 = ℎ𝑣
Photoelectric Effect
- The photoelectric effect provides evidence
for the particle nature of light.
- It also provides evidence for quantization.
- If light shines on the surface of a metal, there
is a point at which electrons are ejected from
the metal.
- The electrons will only be ejected once the
threshold frequency is reached.
- Below the threshold frequency, no electrons
are ejected.
- Above the threshold frequency, the number
of electrons ejected depend on the intensity
Particle as Waves
Basics of Quantum Mechanics
- Aharonov – Bohm Effect –
Quantum Mechanics
- Quantum Mechanics is nothing more but
linear algebra and Hilbert spaces
- What makes quantum mechanics quantum
mechanics is the physical interpretation of
the results that are obtained
First postulate of Quantum mechanics:
Every physically-realizable state of the
system is described in quantum mechanics by a state
function  that contains all accessible physical
information about the system in that state.
- Physically realizable states ➔ states that
can be studied in laboratory
- Accesible information ➔ the information
we can extract from the wavefunction
- State function ➔ function of position,
momentum, energy that is spatially localized.
If 1 and 2 represent two physically-realizable
states of the system, then the linear combination
𝜓 = 𝐶1 𝜓1 + 𝐶2 𝜓2
where c1 and c2 are arbitrary complex constants,
represents a third physically realizable state of the
system.
Wavefunction (x,t) ➔ position and time probability
amplitude
Quantum mechanics describes the outcome of an
ensemble of measurements, where an ensemble of
measurements consists of a very large number of
identical experiments performed on identical non-
interacting systems, all of which have been identically
prepared so as to be in the same state.
Second Postulate of Quantum Mechanics
If a system is in a quantum state represented by a
wavefunction , then
𝑃𝑑𝑉 = |Ψ|4 𝑑𝑉
is the probability that in a position measurement at
time t the particle will be detected in the infinitesimal
volume dV.
The importance of normalization follows from the
Born interpretation of the state function as a position
probability amplitude. According to the second
postulate of quantum mechanics, the integrated
probability density can be interpreted as a probability
that in a position measurement at time t, we will find
the particle anywhere in space.
Limitations on the wavefunction:
Only normalizable functions can represent a quantum
state and these are called physically admissible
functions.
State function must be continuous and single valued
function.
State function must be a smoothly-varying function
(continuous derivative).
Third Postulate

Every observable in quantum mechanics is represented by an operator which is used to

obtain physical information about the observable from the state function. For an
observable that is represented in classical physics by a function Q(x,p), the corresponding
 
operator is Q( x, p) .
Observable Operator

Position x
Momentum   
p=
i x
Energy 
p2  2 2
E= + V ( x) = − + V ( x)
2m 2m x 2
➢ An operator is an instruction, a symbol which tells us to perform one or more
mathematical acts on a function, say f(x). The essential point is that they act on a
function.
➢ Operators act on everything to the right, unless the action is constrained by brackets.
➢ Addition and subtraction rule for operators:

( 
)  
Q1  Q2 f ( x) = Q1 f ( x)  Q2 f ( x)
➢ The product of two operators implies succesive operation:
   

Q1Q2 f ( x) = Q1 Q2 f ( x) 
➢ The product of two operators is a third operator:
  
Q3 = Q1Q2
➢ Two operators commute if they obey the simple operator expression:
 
 
     
Q1, Q2 = Q1Q2 − Q2Q1 = 0  Q1Q2 = Q2Q1
 