Atomic Structure
Atomic Structure
Atomic Structure
Importance of the
Hydrogen Atom
The hydrogen atom is the only
atomic system that can be solved
exactly
Much of what was learned in the
twentieth century about the
hydrogen atom, with its single
electron, can be extended to such
single-electron ions as He+ and
More Reasons the Hydrogen
Atom is Important
The hydrogen atom is an ideal
system for performing precision
tests of theory against
experiment
Also for improving our understanding of atomic structure
Paschen series:
1
R
1 1
H 2 2 n 5 , 6 , 7 ,
λ 4 n
Brackett series:
Joseph John Thomson
1856 – 1940
English physicist
Received Nobel Prize in 1906
Usually considered the
discoverer of the electron
Worked with the deflection
of cathode rays in an electric
field
Opened up the field of subatomic
particles
Early Models of the Atom,
Thomson’s
J. J. Thomson established
the charge to mass ratio for
electrons
His model of the atom
A volume of positive charge
Electrons embedded throughout
the volume
Rutherford’s Thin Foil
Experiment
Experiments done in 1911
A beam of positively
charged alpha particles hit
and are scattered from a
thin foil target
Large deflections could not
be explained by Thomson’s
model
Early Models of the Atom,
Rutherford’s
Rutherford
Planetary model
Based on results of thin foil
experiments
Positive charge is
concentrated in the center of
the atom, called the nucleus
Electrons orbit the nucleus like
planets orbit the sun
Difficulties with the
Rutherford Model
Atoms emit certain discrete characteristic
frequencies of electromagnetic radiation
The Rutherford model is unable to explain this phenomena
Rutherford’s electrons are undergoing a
centripetal acceleration
It should radiate electromagnetic waves of the same frequency
The radius should steadily decrease as this radiation is given off
The electron should eventually spiral into the nucleus
It doesn’t
Niels Bohr
1885 – 1962
Danish physicist
An active participant in the
early development of
quantum mechanics
Headed the Institute for
Advanced Studies in
Copenhagen
Awarded the 1922 Nobel
Prize in physics
For structure of atoms and the
radiation emanating from them
The Bohr Theory of Hydrogen
In 1913 Bohr provided an
explanation of atomic spectra that
includes some features of the
currently accepted theory
His model includes both classical
and non-classical ideas
He applied Planck’s ideas of
quantized energy levels to
Bohr’s Theory, cont.
This model is now considered
obsolete
It has been replaced by a
probabilistic quantum-mechanical
theory
The model can still be used to
develop ideas of energy
quantization and angular
Bohr’s Assumptions for
Hydrogen, 1
The electron moves in
circular orbits around
the proton under the
electric force of
attraction
The Coulomb force produces
the centripetal acceleration
Bohr’s Assumptions, 2
Only certain electron orbits are
stable
These are the orbits in which the atom does not emit energy in the form of
electromagnetic radiation
Therefore, the energy of the atom remains constant and classical mechanics
can be used to describe the electron’s motion
This representation claims the centripetally accelerated electron does not emit
energy and therefore does not eventually spiral into the nucleus
Bohr’s Assumptions, 3
Radiation is emitted by the atom when the electron
makes a transition from a more energetic initial
state to a lower-energy orbit
The transition cannot be treated classically
The frequency emitted in the transition is related to the change in
the atom’s energy
The frequency is independent of frequency of the electron’s
orbital motion
The frequency of the emitted radiation is given by
Ei – Ef = hƒ
If a photon is absorbed, the electron moves to a higher energy level
Bohr’s Assumptions, 4
The size of the allowed electron
orbits is determined by a
condition imposed on the
electron’s orbital angular
momentum
The allowed orbits are those for
which the electron’s orbital
angular momentum about the
Mathematics of Bohr’s
Assumptions and Results
Electron’s orbital angular momentum
mevr = nħ where n = 1, 2, 3,…
The total energy of the atom is
2
1 e
E K U mev 2 ke
2 r
The total energy can also be expressed as
kee 2
E
2r is negative, indicating a bound electron-
Note, the total energy
proton system
Bohr Radius
The radii 2of2 the Bohr orbits are
n
quantized
rn
mke 2
n 1, 2, 3 ,
e e
This shows that the radii of the allowed orbits have discrete values—they are
quantized
When n = 1, the orbit has the smallest radius, called the Bohr radius, ao
ao = 0.052 9 nm
Radii and Energy of Orbits
A general expression
for the radius of any
orbit in a hydrogen
atom is
rn = n2ao
The energy of any orbit
is
k ee 2 1
En 2 n 1, 2,3,
2ao n
This becomes
En = - 13.606 eV / n2
Specific Energy Levels
Only energies satisfying the
previous equation are allowed
The lowest energy state is called
the ground state
This corresponds to n = 1 with E = –13.606 eV
PLAY
ACTIVE FIGURE
Frequency of Emitted Photons
The frequency of the photon
emitted when the electron makes
a transition
Ei Ef kefrom
e 2 1 an1 outer orbit to
ƒ 2 2
an inner h orbit
2ao h is
nf ni
Z is the atomic number of the element and is the number of protons in the
nucleus
Difficulties with the Bohr
Model
Improved spectroscopic
techniques found that many of
the spectral lines of hydrogen
were not single lines
Each “line” was actually a group of lines spaced very close together
πao
According to quantum
mechanics, the atom has no
sharply defined boundary as
suggested by the Bohr theory
Electron Clouds
The charge of the electron is
extended throughout a
diffuse region of space,
commonly called an electron
cloud
This shows the probability
density as a function of
position in the xy plane
The darkest area, r = ao,
corresponds to the most
probable region
Wave Function of the 2s state
The next-simplest wave function
for the hydrogen atom is for the
2s state
n = 2; ℓ = 0
The normalized
1 wave
1 function
r is 3
2
r
ψ2s (r ) 2 e 2 ao
4 2π ao ao
PLAY
ACTIVE FIGURE
Physical Interpretation of ℓ
The magnitude of the angular
momentum of an electron moving
in a circle of radius
r is
L
L = mevr
The direction of is
perpendicular to the plane of the
circle
The direction is given by the right hand rule
L can equal zero, which causes great difficulty when attempting to apply
classical mechanics to this system
Physical Interpretation of mℓ
The atom possesses an orbital
angular momentum
There is a sense of rotation of the
electron around the nucleus, so
that a magnetic moment is
present due to this μ
angular
momentum
B
There are distinct directions
Physical Interpretation of mℓ, 2
Because the magnetic momentμ
of the atom
L
can be related to the
μ
angular momentum vector, L , the
discrete direction of translates
into the fact that the direction
L of
is quantized
Therefore, Lz, the projection of
along the z axis, can have only
Physical Interpretation of mℓ, 3
The orbital magnetic quantum
number mℓ specifies the allowed
values of the z component of
orbital
angular momentum
Lz =L mℓ
The quantization of the possible
orientations of with respect to
an external magnetic field is often
Physical Interpretation of mℓ, 4
Ldoesnot point in a specific
direction
Even though its z-component is fixed
Knowing all the components is inconsistent with the uncertainty principle
Imagine that
must lie anywhere
L
on the surface of a cone that
makes an angle θ with the z axis
Physical Interpretation of mℓ,
final
θ is also quantized
Its values are specified
through
Lz m
cos θ
L 1
mℓ is never greater than
ℓ, therefore θ can never
be zero
Zeeman Effect
The Zeeman effect is the
splitting of spectral lines in a
strong magnetic field
In this case the upper level,
with ℓ = 1, splits into three
different levels
corresponding to the three
different directions of µ
Spin Quantum Number ms
Electron spin does not come from
the Schrödinger equation
Additional quantum states can be
explained by requiring a fourth
quantum number for each state
This fourth quantum number is
the spin magnetic quantum
number ms
Electron Spins
Only two directions exist for
electron spins
The electron can have spin
up (a) or spin down (b)
In the presence of a
magnetic field, the energy of
the electron is slightly
different for the two spin
directions and this produces
doublets in spectra of
certain gases
Electron Spins, cont.
The concept of a spinning electron is conceptually
useful
The electron is a point particle, without any spatial
extent
Therefore the electron cannot be considered to be actually
spinning
The experimental evidence supports the electron
having some intrinsic angular momentum that can
be described by ms
Dirac showed this results from the relativistic
properties of the electron
Spin Angular Momentum
The total angular momentum of a
particular Lelectron state contains
S
both an orbital contribution and
a spin contribution
Electron spin can be described by
a single quantum number s,
whose value can only be s = ½
The spin angular momentum of
Spin Angular Momentum, cont
The magnitude of the spin
angular momentum is
3
S s(s 1)
2
PLAY
ACTIVE FIGURE
Spontaneous Emission
Once an atom is in an
excited state, the
excited atom can make
a transition to a lower
energy level
Because this process
happens naturally, it is
known as spontaneous
emission
Stimulated Emission
In addition to
spontaneous emission,
stimulated emission
occurs
Stimulated emission
may occur when the
excited state is a
metastable state
Stimulated Emission, cont.
A metastable state is a state whose lifetime is
much longer than the typical 10-8 s
An incident photon can cause the atom to return to
the ground state without being absorbed
Therefore, you have two photons with identical
energy, the emitted photon and the incident
photon
They both are in phase and travel in the same direction
Active Figure 42.27
Use the active figure to
adjust the energy
difference between
states
Observe the stimulated
emission
PLAY
ACTIVE FIGURE
Lasers – Properties of
Laser Light
Laser light is coherent
The individual rays in a laser beam maintain a fixed phase relationship with
each other
The tube contains the atoms that are the active medium
An external source of energy pumps the atoms to excited
states
The mirrors confine the photons to the tube
Mirror 2 is only partially reflective
Energy-Level Diagram for
Neon in a Helium-Neon Laser
The atoms emit 632.8-
nm photons through
stimulated emission
The transition is E3* to
E2
* indicates a metastable state
Laser Applications
Applications include:
Medical and surgical procedures
Precision surveying and length measurements
Precision cutting of metals and other materials
Telephone communications