QUANTUM THEORY OF THE

ATOM
Contents and Concepts
Light Waves, Photons, and the Bohr Theory
To understand the formation of chemical bonds,
you need to know something about the electronic
structure of atoms. Because light gives us
information about this structure, we begin by
discussing the nature of light. Then we look at the
Bohr theory of the simplest atom, hydrogen.

1. The Wave Nature of Light

2. Quantum Effects and Photons
3. The Bohr Theory of the Hydrogen Atom
 Light theory Faraday suggests
electricity and Photoelectric Effect
magnetism related (supports particle
Newton proposes particle theory interpretation –
of light Hooke Einstein relates to
Maxwell’s Equations
proposes relate light, electricity, Planck’s quanta
wave theory concept)
magnetism
Huyghens’
Principle Hertz detects radio De Broglie proposes
supports Young: 2-slit experiment waves (supports matter has wave-
waves shows wave behavior wave theory) like qualities

Planck puts
idea in
Einstein’s head

1600 1700 1800 1900 1915 1930

Thomson (JJ) discovers electron

Heisenberg
Balmer, Rydberg relate emission Bohr Model Uncertainty Principle
spectrum lines to counting number proposed
“n”

Davisson/G.P. Thomson
Schrödinger (irony!): electron
Wave Model diffraction
Pauli
Exclusion
Principle
Quantum Mechanics and Quantum Numbers
The Bohr theory firmly establishes the concept of
energy levels but fails to account for the details of
atomic structure. Here we discuss some basic
notions of quantum mechanics, which is the theory
currently applied to extremely small particles, such
as electrons in atoms.

4. Quantum Mechanics
5. Quantum Numbers and Atomic Orbitals
A wave is a continuously repeating change or
oscillation in matter or in a physical field.

Light is an electromagnetic wave, consisting of

oscillations in electric and magnetic fields traveling
through space.
A wave can be characterized by its wavelength
and frequency.

Wavelength, symbolized by the Greek letter

lambda, l, is the distance between any two
identical points on adjacent waves.
Frequency, symbolized by the Greek letter nu, n,
is the number of wavelengths that pass a fixed
point in one unit of time (usually a second). The
unit is 1/S or s-1, which is also called the Hertz (Hz).
Amplitude, The maximum
displacement of the vibrating
particle of the given medium
from the mean(equilibrium)
position is defined as
the Amplitude of the
wave. Amplitude is directly
Proportional to the energy of a
wave, a high energy wave has
a high amplitude and a low
energy wave has a
low amplitude.
Wavelength and frequency are related by the wave
speed, which for light is c, the speed of light, 3.00
x 108 m/s.
c = nl
When the
wavelength is
reduced by a
factor of two,
the frequency
increases by
a factor of
two.
The range of frequencies and wavelengths of
electromagnetic radiation is called the
electromagnetic spectrum.
Electromagnetic Radiation (4)

Example: Red light has l = 700 nm.

Calculate the frequency, n.

3.00 x 10 8 m/s
n= c = = 4.29 x 10 14 Hz
l 7.00 x 10 -7 m

• Wave nature of light is shown by classical wave

properties such as
• interference
• diffraction
One property of waves is that they can be
diffracted—that is, they spread out when they
encounter an obstacle about the size of the
wavelength.

In 1801, Thomas Young, a British physicist,

showed that light could be diffracted. By the
early 1900s, the wave theory of light was well
established.
Huygens’ Principle and Diffraction

Huygens’ principle:
Every point on a wave
front acts as a point
source; the wavefront
as it develops is tangent
to their envelope

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Huygens’ Principle and Diffraction

Huygens’ principle is consistent with diffraction:

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 Huygens’ Principle and
the Law of Refraction
As the waves propagate
from each point, they
propagate more slowly in the
medium of higher index of
refraction.
This leads to a bend in the
wavefront and therefore in
the ray.

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 Huygens’ Principle and
the Law of Refraction

The frequency of the light

does not change, but the
wavelength does as it travels
into a new medium.

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A ray of light is incident through glass, with refractive index
1.52, on an interface separating glass and water with
refractive index 1.32. What is the angle of refraction if
the angle of incidence of the ray in glass is 25 °?

What should be the angle of incidence of a light ray

incident through air on the boundary separating air from
water so that the angle of refraction is 30 °?(refractive
index of air is 1 and that of water is 1.32)

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 Huygens’ Principle and
the Law of Refraction

Highway mirages are due to a

gradually changing index of
refraction in heated air.

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 Young’s Double-Slit Experiment

If light is a wave, interference effects will be seen, where

one part of wavefront can interact with another part.
One way to study this is to do a double-slit experiment:

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 Young’s Double-Slit Experiment:
interference

If light is a wave,
there should be an
interference
pattern.

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 Young’s Double-Slit Experiment:
interference
The interference occurs because each point on the screen
is not the same distance from both slits. Depending on the
path length difference, the wave can interfere constructively
(bright spot) or destructively (dark spot).

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 Young’s Double-Slit Experiment:
interference

We can use geometry to find the conditions for constructive

and destructive interference:

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 Young’s Double-Slit Experiment:
interference

Between the maxima and

the minima, the amplitude
varies smoothly.

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 Young’s Double-Slit Experiment:
interference
Since the position of the maxima (except the central one)
depends on wavelength, the first- and higher-order fringes
contain a spectrum of colors.

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 The Visible Spectrum and Dispersion

Wavelengths of visible light: 400 nm to 750 nm

Shorter wavelengths are ultraviolet; longer are infrared

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 The Visible Spectrum and Dispersion

The index of refraction of a

material varies somewhat
with the wavelength of the
light.

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 The Visible Spectrum and Dispersion

Atmospheric rainbows are created by dispersion in tiny

drops of water.

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 24-5 Diffraction by a Single Slit or
Disk

Light will also diffract around a single slit or obstacle.

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 Diffraction by a Single Slit or Disk

The resulting pattern of light and dark stripes is called a

diffraction pattern.
This pattern arises because different points along a slit
create wavelets that interfere with each other just as a
double slit would.

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 Diffraction by a Single Slit or
Disk

The minima of the single-slit diffraction pattern occur when

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 Diffraction Grating

A diffraction grating consists of a large number of equally

spaced narrow slits or lines. A transmission grating has
slits, while a reflection grating has lines that reflect light.
The more lines or slits there are, the narrower the peaks.

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 Diffraction Grating
The maxima of the diffraction pattern are defined by

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 Using a diffraction grating to
measure the wavelength of light
A spectrometer is a device to measure wavelengths of
light accurately using diffraction grating to separate.

Turntable
Collimator C Diffraction grating

Light θ
Telescope T
source
Achromatic Eyepiece
lenses Eye
Cross-wire
 View through Diffraction Grating

 Spectrum of a star
- Procyon
Diffraction grating placed
in front of a methane air
flame
 Failures of Classial Physics

Line spectra of atoms

Black body radiation Li+
Ca2+
Heat capacity of solids
Cu2+
Photoelectric effect
Sr2+
Ba2+
 Types of Spectra
– Continuous spectrum: Produced by solids,
liquids & dense gases produce - no “gaps” in
wavelength of light produced:

– Emission spectrum: Produced by rarefied gases

– emission only in narrow wavelength regions:

– Absorption spectrum: Gas atoms absorb the

same wavelengths as they usually emit and
results in an absorption line spectrum:

PY3P05
Emission
(line) spectra
of some
elements.
Discontinuous
spectra
 The black body spectrum
Measure the radiated power of the emission from some hot object such
as a hot filament at various temperatures and, as Joseph Stephan
showed experimentally in 1879 and
Ludwig Boltzmann showed theoretically using thermodynamic arguments,
you will find that it depends on the fourth power of the filament’s
temperature, e.g., P(T) = sT4.
– The Stephan-Boltzmann law: radiated power is proportional
to T4.
s is Stephan Boltzmann constant 5.67x10 -8 W/m 2 K 4

In 1894 Wilhelm Wein determined that the wavelength of the maximum

black body radiation times the temperature of the black body was a
constant, e.g. lT=2898 mm K.

Unfortunately, at very long wavelengths (low temperatures) the

experimental data disagreed with this result!!!
 The Rayleigh-Jeans Law
Rayleigh in 1900 and with Jeans corrections in 1905
formulated the Rayleigh-Jeans Law in which the
energy density of black body radiation per unit
wavelength interval is proportional to the
temperature divided by the fourth power of the
wavelength.
This worked well in the infrared but when re-written in
terms of frequency it suggests that the energy density
increases without bound as the frequency increases.

For wavelength For frequency

2𝑐𝐾𝐵 𝑇 2𝜈 2 𝐾𝐵 𝑇
𝐵𝜆 (𝑇) = 𝐵𝜈 (𝑇) =
𝜆4 𝑐2

Where: B is the spectral radiance

 UV- Catastrophe

The black bodies do

not radiate immense
amounts of high
frequency light and so
faced the ultraviolet
catastrophe – failure
of the model.

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Wien’s law, also called Wien’s
displacement law, relationship
between the temperature of
a blackbody and the
wavelength at which it emits
the most light.

Wien’s law of the shift of the

radiative power maximum to
higher frequencies as the
temperature is raised
expresses in a quantitative
form commonplace
observations. Warm objects
emit infrared radiation.

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Heat capacity of metals
The atoms in a crystal
vibrate about their
equilibrium positions.
This motion produces
vibrational waves.

The amplitude of
this vibrational
motion increases
as the temperature
increases.
 Einstein contribution
• At high temperatures, all crystalline solids have a specific
heat of 6 cal/K per mole.
•Observations show that at room temperatures and below
the specific heat of crystalline solids is not a universal
constant.

Cv In each of these materials

(Pb,Al, Si,and Diamond)
cal specific heat approaches
6 constant value asymptotically
Kmol
at high T. But at low T’s, the
specific heat decreases
towards zero which is in a
T complete contradiction with
 the above classical result.
Cv = 3R
kB
 Debye Model
Density of States
According to Quantum Mechanics if a particle is constrained;
the energy of particle can only have special discrete energy
values.
it cannot increase infinitely from one value to another.
it has to go up in steps.
 These “steps” can be so small depending on the
system that the energy can be considered as
continuous.
This is the case of classical mechanics.
But on atomic scale the energy can only jump by a
discrete amount from one value to another.

Definite energy levels Steps get small Energy is continuous

In some cases, each particular energy level can be
associated with more than one different state (or
wavefunction )
This energy level is said to be degenerate.

The density of states  ( ) is the number of

discrete states per unit energy interval, and so
that the number of states between and
   d  ( )d
will be .
Quantum Effects and Photons
Planck’s Quantization of Energy (1900)

– According to Max Planck, the atoms of a solid

oscillate with a definite frequency, n.

– He proposed that an atom could have only certain

energies of vibration, E, those allowed by the
formula
E = hn
where h (Planck’s constant) is assigned a value of
6.63 x 10-34 J. s and n must be an integer.
 Quantum Effects and Photons

Planck’s Quantization of Energy.

– The only energies a vibrating atom can have are

hn, 2hn, 3hn, and so forth.

– The numbers symbolized by n are quantum

numbers.
– The vibrational energies of the atoms are said to
be quantized.
– Solved the ultraviolet catastrophe in blackbody
radiation
The photoelectric
effect.
 Quantum Effects and Photons

Photoelectric Effect

– The photoelectric effect is the ejection of electrons

from the surface of a metal when light shines on it.
– Electrons are ejected only if the light exceeds a
certain “threshold” frequency µ0.
– Violet light, for example, will cause potassium to
eject electrons, but no amount of red light (which
has a lower frequency) has any effect.
 Quantum Effects and Photons

By the early part of twentieth century, the wave theory

of light seemed to be well entrenched.
– In 1905, Albert Einstein proposed that light had both
wave and particle properties to explain the
observations in the photoelectric effect.
– Einstein based this idea on the work of a German
physicist, Max Planck.
 Quantum Effects and Photons
Photoelectric Effect

– The energy of the photons proposed by Einstein

would be proportional to the observed frequency,
and the proportionality constant would be Planck’s
constant.

E = hn

– In 1905, Einstein used this concept to explain the

“photoelectric effect.”
The photoelectric
effect.
 Quantum Effects and Photons

Photoelectric Effect

– Einstein’s assumption that an electron is ejected

when struck by a single photon implies that it
behaves like a particle.
– When the photon hits the metal, its energy, hn is
taken up by the electron.
– The photon ceases to exist as a particle; it is said
to be “absorbed.”
 Quantum Effects and Photons
Photoelectric Effect

– The “wave” and “particle” pictures of light should

be regarded as complementary views of the same
physical entity.

– This is called the wave-particle duality of light.

– The equation E = hn displays this duality; E is the
energy of the “particle” photon, and n is the
frequency of the associated “wave.”
 Photoelectric effect

– For a given metal, a

certain amount of
energy is needed to
eject the electron
– This is called the work
function
– Since E=hn, the
photons must have a
frequency higher than
the work function in
order to eject electrons
The saturation current is proportional to the beam intensity
of light that falls on the cathode.

If V becomes negative, the current does not immediately

fall to zero, which suggests that electrons are emitted
with some kinetic energy, of so that some reach the
other electrode despite the electric field he opposes his
movement.
However, for a certain negative value V0, called braking
potential or cut, the photoelectric current is canceled.
The maximum kinetic energy of the photoelectrons is then:
EKmax = eV0
It is independent of the intensity of the light.

Behavior of the braking potential V0 as function of the

frequency μ of the light was studied by Millikan in 1914
and it got a linear graph
 Bohr’s model
In the early 1900s, the atom was understood to
consist of a positive nucleus around which
electrons move (Rutherford’s model).

This explanation left a theoretical dilemma:

According to the physics of the time, an electrically
charged particle circling a center would continually
lose energy as electromagnetic radiation. But this
is not the case—atoms are stable.
In addition, this understanding could not explain
the observation of line spectra of atoms.

A continuous spectrum contains all wavelengths

of light.

A line spectrum shows only certain colors or

specific wavelengths of light. When atoms are
heated, they emit light. This process produces a
line spectrum that is specific to that atom. The
emission spectra of six elements are shown on the
next slide.
In 1913, Neils Bohr, a Danish scientist, set down
postulates to account for
1. The stability of the hydrogen atom
2. The line spectrum of the atom
 Bohr postulates

a) An atom is constituted by an electrical charge

(nucleus) around which they turn to
compensate for that, describing
circumferences.

b) Each electron can not move over any orbit, but

only in that in sufficient numbers (p) in which its
rotational impulse is an integer multiple of h / 2π.
 Bohr postulates
c) When the electron moves on one of its orbits, it
does not radiate energy.

d) An electron can spontaneously jump from one

orbit to another closer to the nucleus. In doing so
its energy decreases in ΔW, and that loss is
emitted in the form of light whose frequent the
electrons is:
Energy-Level Postulate
An electron can have only certain energy values,
called energy levels. Energy levels are quantized.

For an electron in a hydrogen atom, the energy is

given by the following equation:

RH
E=
n2

RH = 2.179 x 10-18 J
n = principal quantum number
Transitions Between Energy Levels
An electron can change energy levels by
absorbing energy to move to a higher energy
level or by emitting energy to move to a lower
energy level.
For a hydrogen electron the energy change is
given by

ΔE = E f  Ei
 1 1 
ΔE = RH  2  2 
n 
 f n i 

RH = 2.179 × 10-18 J, Rydberg constant

The energy of the emitted or absorbed photon is
related to DE:
E photon = ΔE electron = hn
h = Planck' s constant

We can now combine these two equations:

 1 1 
hn =  RH  2  2 
n 
 f n i 
Light is absorbed by an atom when the electron
transition is from lower n to higher n (nf > ni). In this
case, DE will be positive.

Light is emitted from an atom when the electron

transition is from higher n to lower n (nf < ni). In this
case, DE will be negative.

An electron is ejected when nf = ∞.

Energy-level diagram
for the hydrogen atom.
Electron transitions for
an electron in the
hydrogen atom.
 What is the wavelength of the light emitted

? when the electron in a hydrogen atom

undergoes a transition from n = 6 to n = 3?
 1
ΔE = RH  2 
1 
ni = 6 n 2 
 f ni 
nf = 3 hc hc
RH = 2.179 × 10-18 J ΔE = so λ =
λ ΔE

 
 1 1 
ΔE =  2.179 x 10 18 J  2  2  = -1.816 x 10-19 J
3 6 
  34 

6.626 x 10 J  s  2.998 x 10 8 m

 s
λ= = 1.094 × 10-6 m
 19
- 1.816 x 10 J 
Planck
Vibrating atoms have only certain energies:
E = hn or 2hn or 3hn
Einstein
Energy is quantized in particles called photons:
E = hn
Bohr
Electrons in atoms can have only certain values of
energy. For hydrogen:
RH
E=
n2
RH = 2.179 x 10 18 J, n = principal quantum number
 Quantum Mechanics
Bohr’s theory established the concept of atomic
energy levels but did not thoroughly explain the
“wave-like” behavior of the electron.

Current ideas about atomic structure depend on the

principles of quantum mechanics, a theory that
applies to subatomic particles such as electrons.
 Quantum Mechanics
The first clue in the development of quantum
theory came with the discovery of the
de Broglie relation.
– In 1923, Louis de Broglie reasoned that if light
exhibits particle aspects, perhaps particles of
matter show characteristics of waves.
– He postulated that a particle with mass m and a
velocity v has an associated wavelength.

ℎ
𝜆= de Broglie equation
𝑚𝑣
 de Broglie Relation
For a photon that has both wave and particle
characteristics:
E = hn = hc/l (recall c= nl)
E = mc2
mc2 = hc/l or l = h/mc
Since mc is the momentum of a photon, can
we replace this with the momentum of a
particle?
l = h/mv
This suggests that particles have wave-like
characteristics!
 Quantum Mechanics
If matter has wave properties, why are they not
commonly observed?
– The de Broglie relation shows that a baseball
(0.145 kg) moving at about 60 mph (27 m/s) has a
wavelength of about 1.7 x 10-34 m.
34 kgm2
6.63 
l= = 1.7 10 34
10 s
(0.145 kg )(27 m / s ) m
– This value is so incredibly small that such waves
cannot be detected.
 Quantum Mechanics
If matter has wave properties, why are they not
commonly observed?
– Electrons have wavelengths on the order of a few
picometers (1 pm = 10-12 m).
– Under the proper circumstances, the wave character
of electrons should be observable.
– Molecules are of the dimension of a few pm, so the
wave character of electrons is very important in
molecules
 Quantum Mechanics
If matter has wave properties, why are they not
commonly observed?
– In 1927, Davisson and
Germer was
demonstrated that a
beam of electrons,
just like X rays, could
be diffracted by a
crystal.

The X-Ray difraction is actually used for

solid analysis
The electron gun at the top of the column
produces an electron beam that is focused
into a fine spot as small as 1 nm in
diameter on the specimen surface. This
beam is scanned in a rectangular raster
over the specimen and the intensities of
various signals created by interactions
between the beam electrons and the
specimen are measured and stored in
computer memory.
The scanning electron microscopy (SEM)
The transmission electron microscopy (TEM) principle, as
the name suggests, is to use the transmitted electrons; the
electrons which are passing through the sample before they
are collected. As a result, TEM offers invaluable information
on the inner structure of the sample, such as crystal
structure, morphology and stress state information, while
SEM provides information on the sample’s surface and its
composition.
Copyright © Houghton Mifflin Company. All rights reserved. 7 | 87
 Quantum Mechanics
Quantum mechanics is the branch of physics
that mathematically describes the wave
properties of submicroscopic particles.
– We can no longer think of an electron as having
a precise orbit in an atom.
– To describe such an orbit would require knowing
its exact position and velocity.
– In 1927, Werner Heisenberg showed (from
quantum mechanics) that it is impossible to
know both simultaneously.
 Quantum Mechanics
Heisenberg’s uncertainty principle is a
relation that states that the product of the
uncertainty in position (Dx) and the
uncertainty in momentum (mDvx) of a particle
can be no larger than h/4p.
h
(Dx)(mDvx ) 
4p
– When m is large (for example, a baseball) the
uncertainties are small, but for electrons, high
uncertainties disallow defining an exact orbit.
Heisenberg’s Uncertainty
Principle

(Dx)(mDvx )  h
 Heisenberg’s Uncertainty
Principle

It is clear that to locate a particle it is necessary to add all

the contributions of waves whose wave number varies
between zero and infinite and therefore the moment also
varies between zero and infinite That is to say that it is
completely undetermined..
The uncertainty principle tells us that there is a limit on the
precision with which we can determine at the same time the
position and momentum of a particle.
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 Heisenberg’s Uncertainty
Principle
A wave packet is constructed by superposition a number
infinite harmonic waves of different frequencies.

At a given time, the wave function associated with a packet

of waves is given by
2𝜋 2𝜋𝜈
𝐾= =
𝜆 𝑐

The momentum of the particle and the number of waves

are related as
ℎ𝜈 2𝜋𝜈
𝑃= 𝐾=
𝑐 𝑐

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 Proposed exercises
The uncertainty in the momentum Δp of a football thrown by
Tom Brady during the superbowl traveling at 40m/s is
1×10−6 of its momentum. What is its uncertainty in position
ΔX ? Mass=0.40kg
You notice there is 2 mL of water traveling on the football at the
same speed and Δp . Calculate its ΔX .
An electron in that molecule of water traveling at the same speed
has the same Δp . Calculate its ΔX
Comment on the differences in the uncertainty of momentum
between the ball, water, and electron. How does the mass
effect this value?
Taking into account all of the information presented above, can
you state a situation in which the Heisenberg Uncertainty
Principle has little effect on measuring the momentum and
position of one object, but dominates for that of another when
both objects are part of the same system?
 Spherical coordinates
r is the distance of R to 0, r >< 0.

Ө is the same angle used for

cilindric coordenates when r> 0.

φ is the angle between positive z

axis and the segment OR, 0 > φ
< π.

x = rsenӨcos φ
y = rsenӨsen φ
z = rcos φ
Spherical coordinates (r, θ, φ) as often
used in mathematics: radial distance r,
azimuthal angle θ, and polar angle φ.
 Quantum Mechanics
Although we cannot precisely define an
electron’s orbit, we can obtain the probability
of finding an electron at a given point around
the nucleus.

– Erwin Schrodinger defined this probability in a

mathematical expression called a wave function,
denoted y (psi).
– The probability of finding a particle in a region of
space is defined by y2.
 Classical wave equation
1 u u
2 2
= 2 u ( x, t ) = cos(2pn t )y ( x)
v t
2 2
x
 y 4p n
2 2 2
 y ( x) = 0
x 2
v 2

 y 4p
2 2
since v=nl  y ( x ) = 0
x 2
l 2

y ( x) = A cos(2p x / l )
 Schrodinger equation

mv 2
E=  V ( x), rearrange to give mv={2m[E-V ( x)]}1/ 2
2
h h
de Broglie relation l = =
mv {2m[E-V ( x)]}1/ 2
 2y 4p 2  2y 2m[E-V ( x)]
classical wave eqn.  2 y ( x) = 2  y ( x) = 0
x 2
l x (h / 2p ) 2

(h / 2p ) 2  2y
Schrodinger eqn. -  V ( x)y ( x) = Ey ( x)
2m x 2
Copyright © Houghton Mifflin Company. All rights reserved. 7 | 101
 Postulates of Quantum
Mechanics
The state of a quantum mechanical system is completely
specified by its wavefunction, Y(x,t)
To every classical observable there corresponds a linear,
Hermitian operator in quantum mechanics
In any measurement associated with an operator, the only
values observed are eigenvalues of the operator,
A Y(x,t) = a Y(x,t)
The average values of an observable is given by its
expectation value, 
A =  Y AYd
*

The wavefunction obeys the time dependent Schrodinger
equation, h Y ( x, t )
i = H Y ( x, t )
2p t
 The wavefunction
The square of the wavefunction |Y|2 is the
probability density for finding the particle at that
location
The wavefunction must be
– Single valued
– Continuous
– Continuous first derivative
– Quadratically integrable

 Y Yd must be finite
*

 The Variational Energy
It can be easily proven that the variational energy is always
greater than or equal to the exact energy of the lowest
energy state 
 Y H Yd
*

Evar = 

 Eexact
 Y Yd
*

If we start with an approximate wavefunction and vary it so
as to minimize the energy, we obtain a better wavefunction
and energy
With enough flexibility in the wavefunction, we can get very
close to the exact energy
 Particle in a 1-Dimensional Box
Schrodinger equation
Hy = Ey ,
(h / 2p ) 2  2
H =  V ( x)
2m x 2

outside the box V ( x) = ,

y ( x) = 0
inside the box V ( x) = 0,
np x
1/ 2
2
y ( x) =   sin( )
l l
n2h2
E= 2
, n = 1, 2,...
8ml
.Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines,
7–106
 Hydrogen-like Atom
Nucleus with charge Ze at origin,
Electron with charge -e at (x,y,z) or (r, , )
Schrodinger equation for hydrogen-like atom
Hy = Ey ,
(h / 2p ) 2  2 2  2  Ze 2
H =  x 2  y 2  z 2   4p r
2m   0

(h / 2p ) 2  2 2   1 Ze 2
H =  r 2 r r  2mr 2  4p r
  L2

2m   0

  2
 1  2

L = (h / 2p )  2  cot 
2 2
 2 2
    sin   
Hamiltonian
Wave function ᴪ: "describes the
wave properties of the particle
(electron)
"" is simply a function math
• It is not observable. (Doesn´t
have physical meaning)
"" can be real or imaginary (in the
sense mathematical).
• if it is real corresponds to the
amplitude of the wave (can be +
or -)

Probability density ᴪ2: is the

probability of finding the electron in
a small volume element dV
The wave function for the
lowest level of the
hydrogen atom is shown
to the left.

Note that its value is

greatest nearest the
nucleus, but rapidly
decreases thereafter. Note
also that it never goes to
zero, only to a very small
value.
 The highest
probability

Probability density for an

electron in hydrogen

Probability of finding the electron at

various distances from the nucleus.
 Conditions of ᴪ "to be an acceptable solution:

PRECISE (one value at each point)

CONTINUOS (the probability can not change abruptly)
• in any point can be equal to 1
• Should be 0 for r = infinity
NORMALIZED ∫ᴪ2dV =1

Quantization of energy E comes determined by the boundary

conditions imposed on ᴪ

ORBITAL: each one of the functions of monelectronic waves that

describe the behavior of the electron. They are the solutions of
the Schrödinger equation
Wavefunctions for Hydrogen-like Atoms
Copyright © Houghton Mifflin Company. All rights reserved. 7 | 116
The resolution of the wave equation requires introducing certain
parameters that are quantum numbers:

1. Principal quantum number (n)

2. Angular momentum quantum number (l)
3. Magnetic quantum number (ml)
The Principal Quantum Number ( n )
Because n describes the most probable distance of the
electrons from the nucleus, the larger the number n is,
the farther the electron is from the nucleus.
n can be any positive integer starting at 1, as n=1
designates the first principal shell.
 The Orbital Angular Momentum
Quantum Number ( l )

The orbital angular momentum quantum number l

determines the shape of an orbital, and therefore the
angular distribution.
The number of angular nodes is equal to the value of the
angular momentum quantum number l
Each value of l indicates a specific s, p, d, f subshell
Subshells are sometimes designated by lowercase
letters:

l 0 1 2 3 ...
Letter s p d f
n≥ 1 2 3 4

Not every subshell type exists in every shell. The

minimum value of n for each type of subshell is
shown above.
Magnetic Quantum Number, ml
This quantum number distinguishes orbitals of a
given n and l—that is, of a given energy and shape
but having different orientations.

The magnetic quantum number depends on the

value of l and can have any integer value from –l
to 0 to +l. Each different value represents a
different orbital. For a given subshell, there will be
(2l + 1) values and therefore (2l + 1) orbitals.
The figure
shows
relative
energies for
the hydrogen
atom shells
and
subshells;
each orbital
is indicated
by a dashed-
line.
 Atomic Orbital Shapes

An s orbital is spherical.

A p orbital has two lobes along a straight line

through the nucleus, with one lobe on either side.

A d orbital has a more complicated shape.

The cross-sectional view
of a 1s orbital and a
2s orbital highlights the
difference in the two
orbitals’ sizes.
The cutaway diagrams
of the 1s and 2s orbitals
give a better sense of
them in three
dimensions.
Shape of the three p orbitals
Shape of the five d orbitals
 Electron Spin Quantum Number (ms)
This means that when ms is positive the electron has an
upward spin, which can be referred to as "spin up."
When it is negative, the electron has a downward spin, so it
is "spin down."
The significance of the electron spin quantum number is its
determination of an atom's ability to generate a magnetic
field or not.
 Multielectronic atoms
The repulsion between electrons translates in which the
electrons in a multielectronic atom try to stay away of
others and their movements are entangled with each
other.

In multielectronic atoms, the attractive force of the nucleus

to a given electron increases with the nuclear charge.

In the atoms multielectronics, the energies of the orbitals

depend on the type of orbital; the Orbitals with different
values of E within the same main layer are not
degenerate.
 Penetration and shielding

The electrons in the orbitals closest to the nucleus shield

the core of the most external electrons. In effect, electron
shielding reduces the efficiency of the attraction of the
nucleus makes the electron more distant.

The reduction of the nuclear charge depends on the type of

orbitals in which they are located

The electrons in the orbitals are more effective in shielding

the nucleus to the most external electrons, that the
electrons in the orbitals p or d. This ability is called
penetration. An electron in an orbital with good
penetration shields better than one with low penetration.
The radial portion of the wavefunction really only tells us if
there is high or low probability at various distances from
the nucleus.
Multiplying this probability by the area available at that
distance will give us the Radial Distribution Function
for the given electron. The concentric spherical shells
have areas equal to the surface area of a sphere which
is 4πr2.
 The effective nuclear charge
The magnitude of the shielding effect is difficult to calculate
precisely. As an approximation, we can estimate the
effective nuclear charge on each electron.

The effective nuclear charge (often symbolized as Zeff or

Z*) is the net positive charge experienced by an electron
in a multi-electron atom. The term “effective” is used
because the shielding effect of negatively charged
electrons prevents higher orbital electrons from
experiencing the full nuclear charge.
Copyright © Houghton Mifflin Company. All rights reserved. 7 | 136
 Electronic configuration
The energy of atomic orbitals increases as the principal
quantum number, n, increases. In any atom with two or
more electrons, the repulsion between the electrons
makes energies of subshells with different values
of l differ so that the energy of the orbitals increases
within a shell in the order s < p < d < f.
The arrangement of electrons in the orbitals of an atom is
called the electron configuration of the atom. We
describe an electron configuration with a symbol that
contains three pieces of information The number of the
principal quantum shell, n,
The letter that designates the orbital type (the subshell, l),
and A superscript number that designates the number of
electrons in that particular subshell.
 Rules for the distribution of
electrons in orbitals
1. The electrons occupy the orbitals in a way that
minimizes the energy of the atom.
2. The principle of exclusion of Pauli: two
electrons of an atom can not have the four
equal quantum numbers.
3. Hund’s principle: When there are orbitals with
the same energy (degenerate), the electrons
occupy initially these orbitals individually.
 The Aufbau principle
Aufbau is a German word meaning "progressive
construction", and we will use this method to
assign the electronic configurations to the
elements in order of their number atomic
credential
When we move from one atom to the next, we add
a proton and some neutrons to the nucleus and
then we describe the orbital where the added
electron goes.
Copyright © Houghton Mifflin Company. All rights reserved. 7 | 141
Electronic configurations and the
periodic table