ATOMIC STRUCTURE

ELECTROMAGNETIC RADIATION

subatomic particles (electron, photon, etc)

have both PARTICLE and WAVE properties
Light is electromagnetic radiation -
crossed electric and magnetic waves:
Properties :
Wavelength, (nm)
Frequency, (s-1, Hz)
Amplitude, A
constant speed. c
3.00 x 108 m.s-1
Electromagnetic Radiation (2)

wavelength
Visiblelight

Amplitude

wavelength Node
Ultavioletradiation
 Electromagnetic Radiation (3)

All waves have: frequency and wavelength

symbol: Greek letter nu) Greek
lambda)
units: cycles per sec = Hertz distance (nm)

All radiation: = c

where c = velocity of light = 3.00 x 108 m/sec

Note: Long wavelength

small frequency
Short wavelength
high frequency increasing increasing
frequency wavelength
Electromagnetic Radiation (4)

Example: Red light has = 700

nm.
Calculate the frequency, .
3.00 x 10 8 m/s
= c = 4.29 x 10 14 Hz
7.00 x 10 -7 m

Wave nature of light is shown by classical wave properties

such as
interference
diffraction
 Quantization of Energy
Max Planck (1858-1947)
Solved the ultraviolet
catastrophe

4-HOT_BAR.MOV

Plancks hypothesis: An object can only gain or

lose energy by absorbing or emitting radiant
energy in QUANTA.
 Quantization of Energy (2)

Energy of radiation is proportional to

frequency.
E = h
where h = Plancks constant = 6.6262 x 10-34 Js

Light with large (small ) has a small E.

Light with a short (large ) has a large E.

 Photoelectric Effect
Albert Einstein (1879-1955)
Photoelectric effect demonstrates the
particle nature of light.

No e- observed until light

of a certain minimum E is used.

Number of e- ejected does NOT

depend on frequency, rather it
depends on light intensity.
 Photoelectric Effect (2)

Classical theory said that E of ejected

electron should increase with increase
in light intensity not observed!

Experimental observations can be

explained if light consists of
particles called PHOTONS of
discrete energy.
 Energy of Radiation
PROBLEM: Calculate the energy of
1.00 mol of photons of red light.
= 700 nm = 4.29 x 1014 sec-1
E = h
= (6.63 x 10-34 Js)(4.29 x 1014 sec-1)
= 2.85 x 10-19 J per photon
E per mol = (2.85 x 10-19 J/ph)(6.02 x 1023 ph/mol)
= 171.6 kJ/mol

- the range of energies that can break bonds.

 Atomic Line Spectra

Bohrs greatest contribution to

science was in building a
simple model of the atom.
It was based on understanding
the SHARP LINE SPECTRA
of excited atoms.
Niels Bohr (1885-
1962)
(Nobel Prize, 1922)
 Line Spectra of Excited Atoms
Excited atoms emit light of only certain wavelengths
The wavelengths of emitted light depend on the
element.

Hg

Ne
 Atomic Spectra and Bohr Model
One view of atomic structure in early 20th century was that an
electron (e-) traveled about the nucleus in an orbit.

Electron
+ orbit
1. Classically any orbit should be
possible and so is any energy.

2. But a charged particle moving in

an electric field should emit energy.
End result should be destruction!
 Atomic Spectra and Bohr Model (2)

Bohr said classical view is wrong.

Need a new theory now called
QUANTUM or WAVE MECHANICS.
e- can only exist in certain discrete orbits
called stationary states.
e- is restricted to QUANTIZED energy
states.
Energy of state = - C/n2 where
C is a CONSTANT
n = QUANTUM NUMBER, n = 1, 2, 3, 4, ....
 Atomic Spectra and Bohr Model (3)

Energy of quantized state = - C/n2

Only orbits where n =
integral number are
permitted.
Radius of allowed orbitals
= n2 x (0.0529 nm)

Results can be used to

explain atomic spectra.
 Atomic Spectra and Bohr Model (4)

If e-s are in quantized energy H atom

states, then E of states can
have only certain values.
This explains sharp line
spectra.
n=2
E = -C (1/2 )
2

07m07an1.mov

E = -C (1/12) n=1

4-H_SPECTRA.MOV
 Atomic Spectra and Bohr Model (5)
n=2

Energy
Calculate E for e- in H
falling from n=1
n
E== E2
final to n ==-C[(1/1
- Einitial 1 (higher
2
) - (1/2)2] to lower
= -(3/4)C
energy) .
(-ve sign for E indicates emission (+ve for absorption)
since energy (wavelength, frequency) of light can only be +ve
it is best to consider such calculations as E = Eupper - Elower
C has been found from experiment. It is now called R,
the Rydberg constant. R = 1312 kJ/mol or 3.29 x 1015 Hz
so, E of emitted light = (3/4)R = 2.47 x 1015 Hz
and = c/ = 121.6 nm (in ULTRAVIOLET region)
Structure and spectra of
hydrogenic atoms
 Definition
A hydrogenic atom is a one electron
atom or ion of general atomic
number Z:examples are H, He+,
Li2+, and U91+
Polyelectronic atom is an atom or ion
with more than one electron;
examples include all neutral atoms
other than H.
Hydrogenic atoms are important
because their Schoridinger equation
Hydrogenic atoms spectra
H2
Electric Gaseou Dissociated
discharge sH
Emit lights,
discrete f

n1 =1=The lyman series, 2

the balmer series, 3 the
paschen series
N2= n1+
 Hydrogen atom spectra

Visible lines in H atom

High E Low E
Short Long spectrum are called the
High Low BALMER series.

6
5
4
3
Energy

1
Ultra Violet
Lyman
Visible
Balmer
Infrared
Paschen n
1. Calculate the lowest wavenumber and
wavelength for the lyman series
(82.258 cm-1 and 121.57 nm)
2. Calculate the shortest wavelength line
in the Paschen series (821 nm)
The structure of hydrogenic atoms

The coulomb potential energy

r= distance of the electron from the

nucleus
o=vacuum permitivity
Ze= nuclear charge
Hamiltonian for the electron and
nucleus of mass mn

= h/2 = 1.054 ex-

34Js
Counting the electron
density
 Calculate the probability density for 1s-
electron at the nucleus!

Evaluate the probabilitiy density of the

electron at the nucleus for a 2s-electron