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Chapter 7: Quantum Theory and

Atomic Structure

7.1 The Nature of Light

7.2 Atomic Spectra

7.3 The Wave - Particle Duality of Matter and Energy

7.4 The Quantum - Mechanical Model of the Atom


Electromagnetic Radiation
• WAVELENGTH - The
distance (in meters)  c
between identical points
on successive waves. (  )
• FREQUENCY - The
number of waves (or
cycles) that pass through a
particular point per
second. () ENERGY of •AMPLITUDE - The vertical
radiation is function of distance from the midline to a
frequency. peak, or trough in the wave.
Fig. 7.1
Fig. 7.2
Fig. 7.3
The Spectrum of
Electromagnetic Radiation
• The wavelength of visible light
is between 400 and 700
nanometers
• Radio, TV , microwave and
infrared radiation have longer
wavelengths (shorter
frequencies), and lower
energies than visible light.
• Gamma rays and X-rays have
shorter wavelengths (larger
frequencies), and higher
energies than visible light!
Calculation of Frequency from Wavelength
Problem: The wavelength of an x-ray is 1.00 x10 -9 m or 1 nm, what is
the frequency of this x-ray?
Plan: Use the relationship between wavelength and frequency to
obtain the answer. wavelength x frequency = speed of light!

Solution:   = c therefore c /


speed of light (m/s)
frequency(cycles/sec) =
wavelength(m)
3.00 x 108 m/s
frequency = = 3.00 x 1017
cycles/sec
1.00 x 10 m
-9
Different Behaviors of Waves and Particles

Fig. 7.4
Demonstration
of the
Photoelectric
Effect

Fig. 7.7
The Photoelectric Effect - I
• Below the threshold energy,
nothing occurs !
• Above the threshold, the
kinetic energy of the ejected
electrons is proportional to the
frequency of the light.
• Also, when above the
threshold, as intensity of the
light increases, so does the
number of ejected electrons.
• All metals experience this
effect, but each has a unique
threshold frequency.
The Photoelectric Effect - II

• Albert Einstein
– Theorized Photons
– Won Nobel prize - 1921
• Photons have an energy
equal to:
E = h
• h = Plank’s Constant, and
is equal to:
6.6260755 x 10 - 3 4Jsec
Calculation of Energy from Frequency

Problem: What is the energy of a photon of electromagnetic radiation


being emitted by radio station KBSG 97.3 FM ( 97.3 x 108 cycles/sec)?
What is the energy of a gamma ray emitted by Cs137 if it has a frequency
of 1.60 x 1020/s?
Plan: Use the relationship between energy and frequency to obtain the
energy of the electromagnetic radiation (E = hv).
Solution:
EKBSG =hv = (6.626 x 10 -34Js)(9.73 x 109/s) = 6.447098 x 10 -24J

EKBSG = 6.45 x 10 - 24 J

Egamma ray =hv = ( 6.626 x 10-34Js )( 1.60 x 1020/s ) = 1.06 x 10 -13J

Egamma ray = 1.06 x 10 - 13J


Light Has Momentum
• momentum = p = mu = mass x velocity

• p = Plank’s constant / wavelength

• or: p = mu = h/wavelength
• wavelength = h / mu de Broglie’s equation

• de Broglie’s expression gives the wavelength relationship


of a particle traveling a velocity = u !!
The de Broglie Wavelengths
of Several Objects
Substance Mass (g) Speed (m/s)  (m)
Slow electron 9 x 10 - 28 1.0 7 x 10 - 4

Fast electron 9 x 10 - 28 5.9 x 106 1 x 10 -10

Alpha particle 6.6 x 10 - 24 1.5 x 107 7 x 10 -15

One-gram mass 1.0 0.01 7 x 10 - 29

Baseball 142 25.0 2 x 10 - 34

Earth 6.0 x 1027 3.0 x 104 4 x 10 - 63

Table 7.1 (p. 274)


de Broglie Wavelength Calc. - I
Problem: Calculate the wavelength of an electron traveling 1% of the
speed of light ( 3.00 x 108m/s).
Plan: Use the de Broglie relationship with the mass of the electron, and
its speed. Express the wavelength in meters and nanometers.
Solution: electron mass = 9.11 x 10 -31 kg

velocity = 0.01 x 3.00 x 108 m/s = 3.00 x 106 m/s

h 6.626 x 10 - 34Js
wavelength = = =
mxu ( 9.11 x 10 kg )( 3.00 x 10 m/s )
- 31 6

kg m2
J= therefore :
s2
wavelength = 0.24244420 x 10 - 9 m = 2.42 x 10 -10 m = 0.242 nm
Light and Atoms
• When an atom gains a
photon, it enters an excited
state.
• This state has too much
energy - the atom must lose
it and return back down to
its ground state, the most
stable state for the atom.
• An energy level diagram is
used to represent these
changes.
Fig. 7.11 A desktop analogy for the H atom’s energy
Energy Level Diagram

• Energy

Light
Excited States
Emission
photon’s path

Light
Emission

Light
Emission
Ground State
The Line Spectra of Several Elements

Fig. 7.8
Three Series of Spectral Lines
of Atomic Hydrogen

Fig. 7.9
Fig. 7.10
Heisenberg
Uncertainty Principle
• It is impossible to
know simultaneously
both the position and
momentum (mass X
velocity) of a particle
with certainty !
Quantum Mechanical Model of
the Atom

Wave function called ORBITAL based upon


probability of location of electron at any given
moment in time.

ORBITAL given as a set of quantum numbers

No 2 electrons of same atom can have the same


set of 4 quantum numbers!!! (Pauli Exclusion
Principle)
A Radial
Probability
Distribution
of Apples
Fig. 7.15
Quantum Numbers - I
• 1) Principal Quantum Number = n
• Also called the “energy “ quantum number, indicates the
approximate distance from the nucleus .

• Denotes the electron energy shells around the atom, and is


derived directly from the Schrodinger equation.

• The higher the value of “n” , the greater the energy of the
orbital, and hence the energy of electrons in that orbital.

• Positive integer values of n = 1 , 2 , 3 , etc.


Quantum Numbers - II
• 2) Azimuthal = L
• Denotes the different energy sublevels within the
main level “n”
• Also indicates the shape of the orbitals around the
nucleus.

• Positive integer values of L are : 0 ( n-1 )

• n=1 , L=0 n = 2 , L = 0 and 1


n=3,L=0,1,2
Quantum Numbers - III
• 3) Magnetic Quantum Number - mL Also
called the orbital orientation quantum #

• denotes the direction or orientation in a magnetic field - or


it denotes the different magnetic geometries around the
nucleus - three dimensional space
• values can be positive and negative (-L 0 +L)

• L = 0 , mL = 0 L =1 , mL = -1,0,+1

L = 2 , mL = -2,-1,0,1,2
Quantum Numbers
Allowed Values

n 1 2 3 4

L 0 0 1 0 1 2 0 1 2 3

mL 0 0 -1 0 +1 0 -1 0 +1 0 -1 0 +1

-2 -1 0 +1 +2 -2 -1 0 +1 +2
-3 -2 -1 0 +1 +2 +3
Determining Quantum Numbers for an Energy Level
(Like S.P. 7.5)
Problem: What values of the azimuthal (L) and magnetic (m) quantum
numbers are allowed for a principal quantum number (n) of 4? How
many orbitals are allowed for n=4?
Plan: We determine the allowable quantum numbers by the rules given
in the text.
Solution: The L values go from 0 to (n-1), and for n=3 they are:
L = 0,1,2,3. The values for m go from -L to zero to +L

For L = 0, mL = 0
L = 1, mL = -1, 0, +1
L = 2, mL = -2, -1, 0, +1, +2
L = 3, mL = -3, -2, -1, 0, +1, +2, +3

There are 16 mL values, so there are 16 orbitals for n=4!


as a check, the total number of orbitals for a given value of n is n2, so for
Fig 7.16
Radial probability “Accurate” “Stylized” Combined area
distribution representation of the 2p of the three 2p
of the 2p distribution orbitals: 2p x, 2py
distribution and 2p z orbitals

Fig. 7.17
Fig. 7.18
Fig. 7.19
Quantum Numbers Noble Gases
Electron Orbitals Number of Electrons Element
1s2 2 He

1s2 2s22p6 10 Ne

1s2 2s22p6 3s23p6 18 Ar

1s2 2s22p6 3s23p6 4s23d104p6 36 Kr

1s2 2s22p6 3s23p6 4s23d104p6 5s24d105p6 54 Xe

1s2 2s22p6 3s23p6 4s23d104p6 5s24d105p6 6s24f14 5d106p6 86 Rn

1s2 2s22p6 3s23p6 4s23d104p6 5s24d105p6 6s24f145d106p6 7s25f146d10 ?


The Periodic Table of the Elements
H Electronic Structure He
Li Be B C N O F Ne
NaMg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr NbMo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac Rf Ha Sg

Ce Pr Nd PmSm EuGd Tb DyHo Er Tm Yb Lu


Th Pa U Np PuAmCm Bk Cf Es FmMd NoLr

“ S” Orbitals “ P” Orbitals
“ d” Orbitals “ f ” Orbitals

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