ATOMIC AND ELECTRONIC

STRUCTURES
 ATOMIC STRUCTURE
Dalton’s Atomic Theory
• An element is composed of tiny particles called atoms
– All atoms of the same element have the same chemical
properties
• In an ordinary chemical reaction
– There is a change in the way atoms are combined with each
other
– Atoms are not created or destroyed
• Compounds are formed when two or more atoms of
different element combine
 Fundamental Laws of Matter
• There are three fundamental laws of matter
– Law of conservation of mass
• Matter is conserved in chemical reactions
– Law of constant composition
• Pure water has the same composition everywhere
– Law of multiple proportions
• Compare Cr2O3 to CrO3
• The ratio of Cr:O between the two compounds is a small whole
number
Subatomic Particles
Nuclear symbolism

• A is the mass number

A
Z X • Z is the atomic number
• X is the chemical symbol
 Atomic Numbers & Mass Numbers
Same element - same number of p+
Atomic number (Z) = number of p+
1
Atomic mass unit (amu) = 12
(mass of C atom) that
contains 6 p+ and 6 n0.
1 amu = 1.66054 x 10-24 g

Particle Mass Mass Charge

(g) (amu) (atomic units)
e− 9.1093826 x 10-28 0.000548579 −1
p+ 1.67262129 x 10-24 1.00728 +1
n0 1.67492728 x 10-24 1.00866 0
Isotopes and Atomic Weight
Isotopes
• Atoms of the same element with different A.
• equal numbers of p+
• different numbers of n0
Isotones
• Same number of neutron
Isobars
• Same atomic mass but differ in atomic number

1
Hydrogen isotopes: H 1 p+, 0 n0
1
deuterium (D) 2
H 1 p+, 1 n0
1
3
H 1 p+, 2 n0
tritium (T) 1
For most elements, the percent abundance of its
isotopes are constant (everywhere on earth).

The periodic table lists an average atomic weight.

Atomic mass = Σ(fractional abundance)(isotope mass)

Example
Naturally occurring chromium consists of four isotopes. It
is 4.31% 2450Cr, mass = 49.946 amu, 83.76% 2452Cr, mass =
51.941 amu, 9.55% 2453Cr, mass = 52.941 amu, and 2.38%
54Cr, mass = 53.939 amu. Calculate the atomic weight of
24
chromium.
 General features of the atom today.
•The atom is an electrically neutral, spherical entity composed of a positively charged central
nucleus surrounded by one or more negatively charge electrons.

•The atomic nucleus consists of protons and neutrons.

 Quantum Theory and Atomic Structure

The Nature of Light

Atomic Spectra

The Wave-Particle Duality of Matter and Energy

The Quantum-Mechanical Model of the Atom

Electromagnetic Radiation and Matter
EM Radiation Magnetic field

• Oscillating electric and magnetic Electric field

fields.

• Traveling wave
▪ moves through space like the ripples on a pond

• All types (“colors”) have the same velocity

(through a vacuum).
– c = speed of light = 2.99792458 x 108 ms-1 (exact)
 Electromagnetic Radiation and Matter
Wavelength, λ λ
+
Distance between crests.
Length units (m, cm, nm).

Amplitude
distance
0
Amplitude
Top to bottom distance.

-
Frequency, n = number of crests passing a fixed point per
unit time. Inverse time units (s-1).
1 hertz (1 Hz) = 1 s-1
nλ = c
 Electromagnetic Radiation and Matter
E increases from radio waves (low n, long λ)
to gamma rays (high n, short λ)

Frequency (Hz)
1024 1022 1020 1018 1016 1014 1012 1010 108 106 104 102 100

γ-rays Radiowave
X-rays UV IR Microwave Long radio waves
FM AM

10-16 10-14 10-12 10-10 10-8 10-6 10-4 10-2 100 102 104 106 108
Wavelength (m)

Bacterial Animal Thickness Width Dog

Atom Virus
cell cell of a CD of a CD

Visible light is a
very small portion
400 450 500 550 600 650 700
Wavelength (nm) of the entire spectrum
Regions of the electromagnetic spectrum.
 Electromagnetic Radiation
• In 1900 Max Planck studied black body
radiation and realized that to explain the
energy spectrum he had to assume that:
1. energy is quantized
2. light has particle character
• Planck’s equation is
hc
E = h n or E =

h = Planck’s constant = 6.626 x 10-34 J  s
 Planck’s Quantum Theory
Heated solid objects emit visible light
• Intensity and color distribution depend on T

Increasing filament T
The Photoelectric Effect
• Light can strike the surface of some metals
causing an electron to be ejected.

17
 The Photoelectric Effect

“Light” can cause ejection of e-

from a metal surface.

Metal cathode (-)

An anode (+) attracts e-.

Current is measured. vacuum

window
Anode (+)
The Photoelectric Effect
• What are some practical uses of the photoelectric
effect?
– Electronic door openers
– Light switches for streetlights
– Exposure meters for cameras
• Albert Einstein explained the photoelectric effect
– Explanation involved light having particle-like
behavior.
– Einstein won the 1921 Nobel Prize in Physics for
this work.
19
 The Bohr Model of the Hydrogen Atom
• Heated solid objects emit continuous spectra.
• Excited atomic gases emit line spectra.
• Each element has a unique pattern.

Hydrogen, H

400 500 600 700

wavelength (nm)

Mercury, Hg

400 500 600 700

wavelength (nm)
The line spectra
of several
elements.
Flame Color of Some Metal ions
METAL ION FLAME COLOR
Na+ Yellow
Li+ Red
K+ Violet
Rb+ Red
Cs+ Blue
Ca2+ Orange-Red
Sr2+ Brick red
Ba2+ Yellow-Green
Cu2+ Green
 Flame tests.

strontium 38Sr copper 29Cu

Emission and absorption spectra of sodium atoms.

 The Bohr Model of the Hydrogen Atom
Neils Bohr (1913):
• e- orbit the nucleus.
• e- have fixed E (quantized).
• E-levels are identified with integers, n (n = 1…).
• Unexcited H atom = e- in the lowest level (n = 1)
▪ the ground state.

• Ionized atom (e- removed) has E = 0 (n = ).

E = −2.179 x 10-18 J 1 n = 1, 2, 3, . . .
n2
 The Bohr Model of the Hydrogen Atom
ir emission n
∞
3 absorption: ΔE > 0, n ↑
emission: ΔE < 0, n ↓
2
visible emission
Bohr’s model exactly
Energy

absorption predicts the H-atom

spectrum.

400 500 600 700

wavelength (nm)
1
ultraviolet emission
• The Rydberg 1  1 1 
equation is an = R  2 − 2 
  n1 n 2 
empirical equation
R is the Rydberg constant
that relates the
wavelengths of the R = 1.097  10 7
m -1

lines in the n1  n 2
hydrogen n’ s refer to the numbers
spectrum. of the energy levels in the
emission spectrum of hydrogen
 The Bohr Model of the Hydrogen Atom

H-atom transitions:

1 1
ΔE = −2.179 x 10-18 nf2 – ni2 J
Calculate the E and wavelength (in nm) for an H-atom n =
4 → n = 2 transition.
ΔE = −2.179 x 10-18 [(½)2 −(¼)2 ] J
= −4.086 x 10-19 J
= 4.086 x 10-19 J
(negative sign omitted. Losing energy = emission)

n = ΔE/h = 4.086 x 10-19 J /6.626 x 10-34 Js

= 6.166 x 1014 s-1 = 6.166 x 1014 Hz

λ = c/n = 2.9979 x 108 ms-1/6.166 x 1014 s-1

λ = 4.862 x 10-7 m = 486.2 nm
 Beyond the Bohr Model: Quantum Mechanics
De Broglie (1924): all moving objects act as waves:
h
λ =
mv
λ = wavelength (m) h = Planck’s constant (J s)
m = mass (kg) v = velocity (m s-1)

Davidson and Germer (1927) observed e-

diffraction by metal foils.
• Wave-like behavior!
 Beyond the Bohr Model: Quantum Mechanics
Heisenberg Uncertainty Principle
It is impossible to know both the exact position
and exact momentum of an e-.
h
Dx * mDu ≥
4p
Why?
• Objects only seen by “light” with λ ≤ object size.
• Electrons are very small. Short λ is required.
• Short λ = high n = high E.
• Energetic collisions alter the speed and direction of the
e-.
 Beyond the Bohr Model: Quantum Mechanics
Schrödinger equation (1926):
• Treats e- as standing waves (not particles).
• Developed by analogy to classical equations for the
motion of a guitar string.
• Called “wave mechanics” or “quantum mechanics”
▪ Explains the structure of all atoms and molecules.
▪ Complicated math; important results.

The solutions are energies and mathematical functions

(wave functions, ).
 The Schrödinger Equation

HY = EY

wave function mass of electron potential energy at x,y,z

d2Y d2Y d2Y 8p2mQ

2
+ 2
+ 2
+ (E-V(x,y,z)Y(x,y,z) = 0
dx dy dz h2

how  changes in space total quantized energy of the

atomic system
 The Quantum Mechanical
Picture of the Atom
Basic Postulates of Quantum Theory
1. Atoms and molecules can exist only in certain
energy states. In each energy state, the atom
or molecule has a definite energy. When an
atom or molecule changes its energy state, it
must emit or absorb just enough energy to
bring it to the new energy state (the
quantum condition).
2. Atoms or molecules emit or absorb radiation
(light) as they change their energies. The
frequency of the light emitted or absorbed is
related to the energy change by a simple
equation.

hc
E = hn =

3. The allowed energy states of atoms and
molecules can be described by sets of
numbers called quantum numbers.
• Quantum numbers are the solutions of the
Schrodinger, Heisenberg & Dirac equations.
• Four quantum numbers are necessary to
describe energy states of electrons in
atoms.
 Beyond the Bohr Model: Quantum Mechanics

2 = probability of finding an e- at a point in space.

An electron density (probability) map plots 2 for each
point in space.

Bigger value = darker shade.

 Beyond the Bohr Model: Quantum Mechanics
Each  describes a different energy level.
• H-atom wavefunction () = an orbital.
• e- do not follow fixed orbits around the nucleus.

Probability maps are hard to draw.

• Boundary surfaces are used
▪ contain the e- 90% of the time.
▪ Why not 100%? – it would include the entire
universe!
The H-atom
ground-state
orbital
Electron probability in the ground-
state H atom.
 Quantum Numbers and Atomic Orbitals

An atomic orbital is specified by three quantum numbers.

n the principal quantum number - a positive integer

l the angular momentum quantum number - an integer from 0 to n-1

ml the magnetic moment quantum number - an integer from -l to +l

ms the spin quantum number - +1/2 or -1/2

 Quantum Numbers
Each orbital () includes three quantum numbers:
n, l, and ml

Principal quantum number, n (n = 1, 2, 3, … )

• Most important in determining the orbital energy.
• Defines the orbital size.
• Orbitals with equal n are in the same shell.
 Quantum Numbers
Azimuthal quantum number, l (l = 0 to n −1)
• Defines the shape of an orbital.
• Orbitals with equal l (and equal n) are in the same
subshell.
• Code letters identify l

l 0 1 2 3 4 5 ...
Code s p d f g h ...
 Quantum Numbers
Magnetic quantum number, ml (ml = –l to +l )
• Defines the orientation of the orbital.
Example
List all sets of quantum numbers for an n = 3 e-.
l = 0, or 1, or 2
if n = 3 and l = 2 (3d), ml is -2, -1, 0, 1 or 2.
if n = 3 and l = 1 (3p), ml is -1, 0, or 1.
if n = 3 and l = 0 (3s), ml must be 0.

Every (n, l, ml) set has a different shape and/or

orientation.
 Quantum Numbers
Number of Number of Maximum
Electron Subshell Orbitals Electrons Electrons
Shell type Available Possible for nth Shell
(n) (=2l + 1) in Subshell (=2n2)

1 s 1 2 2
2 s 1 2
p 3 6 8
3 s 1 2
p 3 6
d 5 10 18
4 s 1 2
p 3 6
d 5 10
f 7 14 32
5 s 1 2
p 3 6
d 5 10
f 7 14
g* 9 18 50
 Electron Spin
Experiments showed a 4th quantum no. was needed

spin quantum number, ms

• +½ or −½ only.

View an e- as a spinning sphere.

Spinning charges act as magnets.

• Pauli: every e- in an atom must have a unique set of (n, l,

ml, ms).
▪ Maximum of 2e- per orbital (opposite spins).
▪ Pauli exclusion principle.
 s Orbitals
l = 0 orbital:
Every shell (n level) has one s orbital.
Spherical. Larger n value = larger sphere

Probability of finding e- at
distance r from nucleus
1s 2s 3s

Distance from nucleus, r (pm)

 p Orbitals

Three p orbitals (l = 1): px, py and pz

Related to ml = -1, 0, +1.

The 2p orbitals.
 d Orbitals

Five d orbitals (l = 2):

3dxz 3dxy 3dyz 3dx -y 3d

2 z2 2
The 3d orbitals.