General Chemistry

Electronic Structure
of Atoms
ROSEMAN B. TUMALIUAN
Teacher III Electronic
Structure
of Atoms
 Atoms and Electromagnetic Radiation
Atoms absorb and emit energy, often in the form of electromagnetic radiation
(visible light, microwaves, radio & TV waves, u.v., infrared,etc)

Electronic
Structure
of Atoms
{Fireworks}
 The Nature of Light Energy
(1) White Light is not white, it is colored: the Spectrum:

Spectroscope

(2) Light is electrical

and magnetic
(electromagnetic) VIB G.Y O R
i n l r e r e
(3) Light does not o d u e l a d
travel in truly l i e e l n
straight lines, it e g n o g Electronic
Structure
travels in waves t o w e of Atoms
{3D-Wave}
Light Energy as Waves: two important characteristics
 1. wavelength (): the
short
 = high
distance (m) between
corresponding points on
adjacent waves
 2. frequency () or (f ): the
long  = low number of waves passing
a given point per unit of
time (1/s = s1-)
1 constant (c)
For waves traveling at the same    
 
velocity, the longer the wavelength,
the smaller the frequency
Knowing 
c     (m)  (1/sec)
and , you SPEED = DISTANCE x PER UNITElectronic TIME
Structure
calculate the Speed (c) = wave length (λ) x frequency ()
of Atoms
speed of light m/sec = m x 1/sec
 Electromagnetic Radiation c  
A form of energy characterized by waves (or pulses) of
varying frequencies ( and wavelengths (). c



{*Light Waves}
{3D-Wave}

Electronic
{Wavelength of v. l.} Structure
of Atoms
 Electromagnetic Radiation
Speed of Light: All Einstein’s Theory of
electromagnetic radiation Special Relativity: Energy and
travels at the same velocity (c), mass are different forms of the
3.00  108 m/s. same thing
1
 α

mc2
c
Frequency (f )

Problem: What is the wavelength of a photon of light that has a

frequency of 3.8 x 109 s-1 ?
c 3.00 x 108 m s -1
c  
3.8 x 109 s -1
= 7.89x10-2Electronic
m
Structure
 of Atoms
 The Nature of Energy:
Discrete vs. Continuous
Digital: Analog
0110100101001

Eggs:

Water:

Waves:
Quanta (Photon): Electronic
Structure
of Atoms

particles
Energy as a Particle (Photon, Quanta)
Light
When light energy shines Energy
on a metal, an electron
current is generated.

waves

particles
Light is behaving as
a particle (photon)
that knocks-off
valence electrons Electronic
Structure
from the metal. of Atoms
{Photoelectric Effect}
 Energy as a Particle (Photon, Quanta)
{Metals & EM Radiation}

• The wave nature of light does

not explain how an object can
glow when its temperature
increases.
• Max Planck explained it by
assuming that energy comes in
packets called quanta (energy
bundle, photon). Max Planck (1848-1947)

Planck concluded that energy (E) is proportional to frequency

For any particular frequency () there is a particular
  E  h bundle of Energy (E) that exists as a discrete quantity
(quanta) that is a multiple of Planck’s constant (h).

where h is Planck’s constant, 6.63  10−34 J-s.

Energy from electrons comes in discrete quantities (bundles) that
Electronic
1 Structure
are whole number multiples of h of Atoms
2
The Nature of Energy
c
Since c = then  

c 
E h  h   
 
Therefore, if one knows the wavelength
of light, one can calculate the energy in
one photon, or packet, of that light.

Problem: What is the wavelength

(in Å) of a ray whose energy is
6.16 x 10-14 erg? {Note: Modules Electronic
Structure
use erg =10-7 Joule} of Atoms
 The Nature of Energy
c
E = h  h  

Problem: What is the wavelength (in Å) of a ray whose energy
is 6.16 x 10-21 Joules? {Note: Modules use erg =10-7 Joule}

c  3. 0 x 10 8
m / sec 
  h    6.63 x 10 Joules.sec 
- 34

E
- 21
 6.16 x 10 Joules 

  3.23 x 10 m -5

 1Å 
? Å  3.23 x 10 m
-5 -10
  3 .23 x 10 5
Å Electronic
 10 m  Structure
of Atoms
Electronic
Structure
of Atoms
 Energy as……
(1) Waves

c =  c
   c
 E hE  h    
 
(2) Particle (Photon, Quanta)

 ΔE =h

(3) Matter
Electronic
Structure
mc2 of Atoms
The Wave-Particle Duality of Matter
• Electromagnetic radiation can behave as a {ElectonWaves}
particle or as wave phenomena
• Louis de Broglie posited that if light can
have material properties, matter should
exhibit wave properties.

• He demonstrated that the relationship

between mass (m) and wavelength ()
was:

1 h
∝ m  = mv
velocity (v)
Electronic
(where h is Planck’s constant, 6.63  10−34
J-s, and v is velocity Structure
of Atoms
of light) = eq given
 The Wave Nature of Matter
Problem: An electron has a mass of 9.06 x 10-25 kg and
is traveling at the speed of light. Calculate its
wavelength?
h  (6.63 x 10 -34 J / s )

 = mv
-18
- 25 8
2.44 x10 m
(9.06 x 10 kg ) x (3.00 x 10 m/s)

Problem: What is the wavelength of a 70.0 kg skier

traveling down a mountain at 15.0 m/s?
-34
h 
( 6.63 x 10 J / s )
 6.31 x10 -37 m
 = mv ( 70.0 kg ) x (15.0 m/s) Electronic
Structure
of Atoms
J = Joule = kg.m2
 The Nature of Energy
White Light’s Continuous Spectrum:

VIB G.Y O R
Electronic
Structure
of Atoms
 The Nature of Energy
Substances both absorb and emit only certain Discrete Spectra

{Flame Tests.Li,Na,K} {Na,B} {AtomicSpectra}

Electronic
Structure
of Atoms
 The Bohr “Planetary” Model
of the Atom (1913)
• Niels Bohr adopted Planck’s assumption and explained atomic
phenomena in this way:
1. Electrons in an atom can only occupy certain orbits (corresponding to
certain energies, frequencies and wavelengths, because E=h=h c/λ).
2. Electrons in permitted orbits have specific, “allowed” energies; these
energies will not be radiated from the atom.
2nd EL
1st EL f=5
f=4

3. Energy is only absorbed or emitted in such a way as

to move an electron from one “allowed” energy state Electronic
Structure
to another; the energy is defined by of Atoms
E = h
 The Bohr Model of the Atom
Which series releases most energy?

Electronic
Structure
of Atoms
The larger the fall the
{ExcitedElectrons*} greater the energy
Atomic Spectra & Bohr Atom
The energy absorbed or emitted
from the process of electron
promotion or demotion can be
calculated by the
Rydberg formula for hydrogen (1885)
1 1 1

 RH ( nf2
- 2
ni )
Rydberg formula for hydrogen-like
elements (He+, Li 2+, Be3+ etc., )
1



where RH is the Rydberg constant, 2.18 Electronic

10−18 J,
Structure
and ni and nf are the initial and final energy levels
of Atoms
of the electron. Z is the atomic number
Atomic Spectra & Bohr Atom
Since energy and wavelength are mathematically
related, the Rydberg Equation can also be expressed
in terms of energy:
RH RH
1
 E = RH
1
nf2(-
1
ni2
= )
nf 2
- 2
ni
( )

 2.180 x 10 J   2.180 x 10 J 
-18 -18

E   2
 -  2
  E f  Ei
 nf   ni 
The energy possessed by an electron at a particular energy level
(En) can be expressed as:
-18

2.180 x 10 Joule
En 
n2
 = eq given
Electronic
Structure
where RH is the Rydberg constant, 2.18  10−18 J, and ni and nf are the initial
of Atoms
and final energy levels of the electron.
Atomic Spectra and the Bohr Atom
Problem: How much energy (J) is liberated when an
electron changes from n = 4 to n = 2? What is the
wavelength (m) of the light emitted?
 2.180 x 10-18 J   2.180 x 10-18 J 
  2.180 x 10-18 J   2.180 x 10-18 J 
E  E f  E i  -      -  
 nf2  ni2
 2f2
  4i2

   

E  (0.545 x 10 -18 J) - (0.1362 x 10-18 J)  0.4088 x 10-18 J

To convert energy to wavelength, we must employ the equations:

 c c
c  
E  h  h   
  
c  3 .0 x 10 8
m/s 
  h   6.63 x 10 J.s 
-34
-18
  4.865 x
Electronic
10 -7
m
Structure
E  0.4088 x 10 J  of Atoms
Atomic Spectra and the Bohr Atom
Notice that the wavelength calculated from
the Rydberg equation matches the wavelength
of the green colored line in the H spectrum.

  4.865 x 10-7 m E  0.4088 x 10-18 J

Electronic
Structure
of Atoms
2006 (B)

Ele 1

Electronic
Structure
of Atoms
Ele 2
Heisenberg’s Uncertainty Principle
• Heisenberg showed that the more
precisely the momentum of a particle is
known, the less precisely is its position
known:

h
(x) (mv) 
4

• In many cases, our uncertainty of the

whereabouts of an electron is greater
than the size of the atom itself! Electronic
Structure
of Atoms
 Quantum Model of the Atom
• Max Planck (energy quanta, Planck’s constant)
• Albert Einstein (energy and frequency)
• Niels Bohr (electrons and Spectra)
• Louis de Broglie (particle-wave duality of matter)
• Werner Heisenberg (electron uncertainty)
• Erwin Schrödinger (probability wave function, the four
quantum numbers) Prof. Alonso
• Jörge L. Alônsø (diagrammatic quantum mechanical
atomic model)

Electronic
Solvay Conference in Structure
of Atoms
Brussels 1911
1 Energy 2 Sublevel
3dyz
Levels = Orbital
1, 2, 3, etc types =
s, p, d, f
3s
3pz
3px

2pz
3dxy 2s 2px
3dxz

1s

2py

3dx2y2
3dx 2
3 Orbital cloud 3py
4 Electron pair
Electronic
orientation Structure
spin inof Orbital
Atoms
(x, y, z, etc) cloud (2e- ea)
1 Energy 2 Sublevel
3dyz
Levels = Orbital
1, 2, 3, etc types =
s, p, d, f
3s
3pz
3px

2pz
3dxy 2s 2px
3dxz

1s

2py

3dx2y2
3dx 2
3 Orbital cloud 3py
4 Electron pair
Electronic
orientation Structure
spin inof Orbital
Atoms
(x, y, z, etc) cloud (2e- ea)
 Quantum Numbers
• Describe the location of electrons within atoms.

• There are four quantum numbers:

 Principal = describes the energy level (1,2,3,etc)
Azimuthal = energy sublevel, orbital type (s2, p6,
d10, f14)
Magnetic = orbital orientation or cloud (2
electrons on each cloud) Example: three p clouds:
px, py, pz
Electronic
Spin = which way the electron is spinning (↑↓) ofStructure
Atoms
Electron Configuration, Orbital Notation
and Quantum Numbers
Principal (n)= energy level Azimuzal () = sublevel
orbital type

1s2 2s2 2p6 3s23p63d10 4s24p64d104f14

Spin (ms) =
electron + or -
Magnetic (ml) = orbital
cloud orientation (2e- Electronic
per orbital) Structure
of Atoms
 Electron Configuration
Two issues:
(1)Arrangement of electrons within an atom
1s2 2s2 2p6 3s23p63d10 4s24p64d104f14
(2) Order in which electrons fill the orbitals
1s22s22p63s23p64s23d104p65s24d105p66s24f14
Aufbau Process: Using Periodic Table Sub-
blocks:

Electronic
Structure
of Atoms
Historic Development of Atomic Theory

Bohr (1913) Schrödinger (1926)

Electronic
Structure
of Atoms
The Schrödinger Equation

i • is the imaginary unit, (complex number whose square is a negative real

number)
t
• is time,

• is the partial derivative with respect to t,

• is the reduced Planck's constant (Planck's constant divided by 2π),

ψ(t) • ψ(t) is the wave function,

Electronic
• is the Hamiltonian (a self-adjoint operator acting on the Structure
state space). of Atoms
 Quantum Mechanics
• Developed by Erwin Schrödinger, it
is a mathematical model
incorporating both the wave &
particle nature of electrons.

• The wave function is designated

with a lower case Greek psi ().

• The square of the wave function, 2,

gives a probability density map of
where an electron has a certain
statistical likelihood of being at any
Electronic
given instant in time. Structure
of Atoms
{QuantumAtom}
 The Schrödinger Equation

• Solving the wave equation gives a set of

wave functions ψ(t ,) or orbitals, and
their corresponding energies.
• Each orbital describes a spatial
distribution of electron density.
• An orbital is described by a set of three Electronic

quantum numbers. Structure

of Atoms
 Principal Quantum Number, n

1 2 3

• The principal quantum number, n, describes the

energy level on which the orbital resides.
• The values of n are integers ≥ 0. Electronic
Structure
of Atoms
 Azimuthal Quantum Number, 
• This quantum number defines the shape of the orbital.
• Allowed values of  are integers ranging from 0 to n − 1.
• We also use letter designations:

Value of  0 1 2 3

Type of orbital s p d f

=0 =1 =2 =3

Electronic
Structure
of Atoms
 Magnetic Quantum Number, ml
• Describes the three-dimensional orientation of the
orbital.
• Values are integers ranging from -l to l:
−l ≤ ml ≤ l.
• Therefore, on any given energy level, there can be up
to 1 s orbital, 3 p orbitals, 5 d orbitals, 7 f orbitals, etc.

Electronic
0 Structure
of Atoms
+1 0 -1
 Values of Quantum Numbers
• Principal Quantum #: values of n are integers ≥ 0.
• Azimuthal Quantum #: values of  are integers ranging from 0 to n − 1.
• Magnetic Quantum #: values are integers ranging from -  to  :
−  ≤ ml ≤  .

Electronic
Structure
of Atoms
s Orbitals ( = 0)
Observing a graph of
probabilities of finding
an electron versus
distance from the
nucleus, we see that s
orbitals possess n−1
nodes, or regions
where there is 0
probability of finding
an electron.
Electronic
Structure
of Atoms
{RadialElectronDistribution}
s Orbitals ( = 0)

• Spherical in shape.

• Radius of sphere
increases with
increasing value of n.

Electronic
Structure
{1s} {2s} {3s} of Atoms
 p Orbitals ( = 1)
• Have two lobes with a node between them.

Electronic
Structure
{www.link}
+1 {px} 0 {py} -1 {pz} of Atoms
 Orbital Overlap: 1s2 2s2 2p6

1s  
2s

2p

“P” orbital electrons are

“P” orbital electrons also
repelled by the “S” orbital
repel from each others’
electrons and so spend more
sublevels, so they runElectronic
along
time further from the Structure
the axes. of Atoms
nucleus.
 d Orbitals ( = 2)

-1 2 -2

•Four of the five orbitals

have 4 lobes; the other
resembles a p orbital
with a doughnut around
the center. Electronic
Structure
of Atoms
1 0 {*Orbitals.s.p.d} {www.link}
 f Orbitals ( = 3)
0
• There are seven f
orbitals per n level.
 The f orbitals have
1 -1 complicated names.
 They have an  = 3
 m = -3,-2,-1,0,+1,+2,
+3 7 values of m
-2  The f orbitals have
2
important effects in the
lanthanide and actinide
elements.
Electronic
Structure
of Atoms
3 -3 {www.link.f}
 Energies of Orbitals

• For a one-electron
hydrogen atom, orbitals
on the same energy
level have the same
energy.

• That is, they are

degenerate (collapsed).
Electronic
Structure
of Atoms
Energies of Orbitals
• As the number of
electrons increases,
though, so does the
repulsion between
them.
• Therefore, in many-
electron atoms,
orbitals on the same
energy level are no
longer degenerate. Electronic
Structure
of Atoms
{E.L. vs FillingOrder}
Electron Configuration & Periodic Table

Electronic
Structure
of Atoms
 Spin Quantum Number, ms

• 1920s: it was discovered that two electrons in the

same orbital do not have exactly the same energy.

The “spin” of
an electron
describes its
magnetic
field, which
affects its
Electronic
Structure
energy.
of Atoms
{e-spin}
Electron Configurations
• Distribution of all
electrons in an atom.
• Consist of
 Number denoting the
energy level.
 Letter denoting the type
of orbital.
 Superscript denoting the
number of electrons in
those orbitals.

Electronic
Structure
of Atoms
 Orbital Diagrams
• Each box represents
one orbital.
• Half-arrows represent
the electrons.
• The direction of the
arrow represents the
spin of the electron.

Electronic
Structure
of Atoms
 Basic Principles of Electron
Configuration Notations
• Pauli Exclusion Principle
• Hund’s Rule of Maximum Multiplicity
• Alonso’s Rules of the Stability of Degenerate Orbitals

Electronic
Structure
of Atoms
 Pauli Exclusion Principle
Only two electrons can occupy an orbital and
they must have opposite spins.

• No two electrons in the same atom can have exactly the same
Electronic
Structure
energy (identical sets of quantum numbers) of Atoms
Hund’s Rule of Maximum Multiplicity
One electron fills each orbital before a second of
opposite spin accompanies it.

“For degenerate orbitals, the lowest energy is

attained when the number of electrons with the same
spin is maximized.”
Electronic
Structure
{Electron Configuration} {Electron Configuration2} of Atoms
 Alonso’s Rules of the Stability of
Degenerate Orbitals
s d
Completely Filled Completely Filled

Completely Filled Half Filled

Most Stable
Electron
Configuration Half Filled Half Filled

Completely Filled Not even Half Filled

Electronic
Structure
of Atoms
Phenomenon also occurs between degenerate s and f orbitals
Periodic Table and {e- filling order}

Electron
Configuration

Electronic
Structure
of Atoms
 Nitrogen
Electronic configuration : 1s2 2s2 2p3

4s 3d
3p
3s

2p Hund’s Rule
2s
1 2 GROUP 3 4 5 6 7 0
1 H He

2 Li Be B C N O F Ne

3 Na Mg Al Si P S Cl Ar

1s 4K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Electronic
Structure
of Atoms
 Neon
Electronic configuration: 1s2 2s2 2p6

4s 3d
3p
3s

2p Hund’s Rule
2s
1 2 GROUP 3 4 5 6 7 0
1 H He

2 Li Be B C N O F Ne

3 Na Mg Al Si P S Cl Ar

1s 4K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Electronic
Structure
of Atoms
 Vanadium
Electronic configuration: 1s2 2s2 2p6 3s2 3p6 4s2 3d3

4s 3d
3p [Ar]
3s

2p [Ne]
2s
1 2 GROUP 3 4 5 6 7 0
1 H He

2 Li Be B C N O F Ne

3 Na Mg Al Si P S Cl Ar

1s 4K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Electronic
Structure
of Atoms
 Chromium
Electronic configuration: 1s2 2s2 2p6 3s2 3p6 4s1 3d5

4s 3d
3p [Ar] Notice that one of the 4s electrons
3s has been transferred to 3d so that 3d
is now a half filled shell with extra
stability. 4s and 3d contain only
2p [Ne] unpaired electrons.
2s
1 2 GROUP 3 4 5 6 7 0
1 H He

2 Li Be B C N O F Ne

3 Na Mg Al Si P S Cl Ar

1s 4K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Electronic
Structure
of Atoms
 Nickel
Electronic configuration: 1s2 2s2 2p6 3s2 3p6 4s2 3d8

4s 3d
3p [Ar]
3s

2p [Ne]
2s
1 2 GROUP 3 4 5 6 7 0
1 H He

2 Li Be B C N O F Ne

3 Na Mg Al Si P S Cl Ar

1s 4K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Electronic
Structure
of Atoms
 Copper
Electronic configuration: 1s2 2s2 2p6 3s2 3p6 4s13d10

4s 3d
3p Notice that again one of the 4s electrons
3s has been promoted to 3d so that 3d
is now a completely filled shell with extra
stability.
2p
2s
1 2 GROUP 3 4 5 6 7 0
1 H He

2 Li Be B C N O F Ne

3 Na Mg Al Si P S Cl Ar

1s 4K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Electronic
Structure
of Atoms
 Some Anomalies

Some irregularities occur when there are enough Electronic

Structure
electrons to half-fill s and d orbitals on a given row.
of Atoms
 Some Anomalies
Electron configuration for copper is
[Ar] 4s1 3d5
rather than the expected
[Ar] 4s2 3d4.

•This occurs because the s and d orbitals are very close in energy.
Electronic
Structure
of Atoms
 Some Anomalies
• These anomalies also occur in f-block atoms, as well.

Electronic
Structure
of Atoms
 Electron Configuration
Identify elements which posses the following
electron configurations:
1s2 2s2 2p6 3s2 3p6 4s2 3d6 Fe {Aufbau order of filling}

1s2 2s2 2p6 3s2 3p6 3d6 4s2 Fe {Energy level order}

[Ar] 4s 3d
2 6 Fe {Previous Nobel Gas Abbreviation}

{Cations formed by removal of outermost

[Ar] 4s0 3d6 Fe 2+
electrons}

Electronic

Write Elect-Config for S 2- [Ne] 3s2 3p6 Structure

of Atoms
Electronic
Structure
of Atoms
Periodic Table and {e- filling order}

Electron
Configuration

Electronic
Structure
of Atoms
 Uses dots to represent Valence Electrons =
those in outermost Energy Level

1
2 Transition Metals
3
4
5
6
7
Have additional electrons, but
Electronic
they are in an energy level that is Structure
lower than the valence electrons. of Atoms
Electronic
Structure
of Atoms
Electrons behave as waves (like standing waves above) and particles.
Electron position cannot be pinned down. Electronic
Structure
Electons don’t follow orbits, but rather orbitals describe their paths.
of Atoms
The Energy of Electromagnetic Waves

Einstein concluded that energy (E) is proportional to

frequency
E  h 
where h is Planck’s constant, 6.63  10−34 J-s.
Electronic
h
Energy from electrons comes in whole number multiples ofofStructure
Atoms
 = eq given
The Bohr Model of the Atom (1913)

Electronic
Structure
of Atoms
 The Nature of Energy

• One does not observe a

continuous spectrum, as
one gets from a white light
source.
• Only a line spectrum of Electronic
Structure
discrete wavelengths is of Atoms
observed.
Electronic
Structure
of Atoms
 Atoms and Electromagnetic Radiation
•To understand the electronic structure of atoms, one must
understand the nature of waves.

Atoms absorb and emit energy, often in the form of electromagnetic radiation
(light, microwaves, radio & TV waves, u.v., infrared,etc)

Electronic
Structure
of Atoms
THANK
YOU
