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ELECTRONS IN ATOMS

Wave description of light

Electromagnetic spectrum - made of electromagnetic


radiation (forms of energy that exhibit wavelike
behavior as they travel through space).
Electromagnetic waves - combination of electrical and
magnetic fields which travel at the speed of light

c = 3.00 x 108 m/sec

Wavelength

(lambda) usually measured


in
nm or ngstroms ()

Relative sizes of
wavelengths

Frequency (Greek letter nu) (or f)


units are usually cycles/sec, sec 1, or
Hertz (Hz).

F
r
e
q
u
e
n
c
y

c = = 3.0 x 108 m/sec

www.atmos.washington.edu/~hakim/301/handouts.html

The Photoelectric effect


The emission of
electrons from a
metal when light
shines on the
metal. The
number of
electrons and their
energies depends
on the brightness
of the incident
light.

http://www.astro.virginia.edu/class/oconnell/astr30/im/photoelectric-effect2.jpg

Max Planck (1900)

E=h

He suggested that the object


emits energy in small, specific
amounts called quanta. A
quantum is the minimum
quantity of energy that can be
lost or gained by an atom. He
proposed
E = h where
E = energy in Joules,
= frequency , and
h = Plancks constant;

6.626 x 10-34 Js

What is a Joule?
A Joule is the derived unit of
energy in the SI system. It is
the energy exerted by a force
of one Newton acting to move
an object through a distance of
one meter.

James Prescott
Joule

I Joule = Force x distance =


1 Newton-meter = (mass x acceleration) x
meter=

kg m/s m = kgm /s
2

Einstein and wave-particle duality


(1905)

abyss.uoregon.edu/~js/images/wave_particle.gif

Light particle and wave?


Each particle of light
carries a quantum of
energy which Einstein
called photons. A photon is
a particle of
electromagnetic
radiation having zero mass
and carrying a quantum of
energy.
For an electron to be ejected from the surface of a metal, the metal
surface must be hit by a single photon possessing at least the
minimum energy required to knock the electron loose (multiples of
whole numbers of photons) Each metal has electrons bound to its
surface with different strengths so the minimum frequencies differ
with each metal.

Spectroscopy

ctrum
e
p
S
n
o
si
is
m
-E
e
in
L
Bright
The Hydrogen-atom

Energy of photons emitted


When an excited hydrogen atom falls back
from an excited state (a higher potential
energy than it has in its ground state) to its
ground state (lowest energy state of an
atom) or a lower energy state, it emits a
photon of radiation.

Ephoton = E2-E1

Bohr (Niels) Model of the Atom 1913 The allowed

orbits have
specific
energies, given
by a simple
formula
En = (-RH)
n = 1,2,3,4,. . .
RH is the
Rydberg
constant
2.18 x 10-18 J

Evidence for Electrons in Fixed-Energy Levels

The collection of narrow


bands of light energy is
referred to as an emission
line spectrum, and the
individual bands of light
are called spectral lines.
The concept of electron
energy levels is supported
by spectral lines.

Combining equations
Given: E = h and E = E2-E1
combining them results in
= E = ( RH) (1 - 1 )
h
h
n 2i n 2f
Further simplification:

= ( RH) (1 - 1 )
n 2i n 2f

Bohr Model of the atom

Electrons in hydrogen atoms exist in only


specified energy states.
Electrons in hydrogen atoms can absorb
only certain specific amounts of energy
and no others.
When the excited electrons in a hydrogen
atom lose energy, they lose only specific
amounts of energy as photons.
Different photons produce different color
lines as seen in a bright line-emission
spectrum.
The main problem was that this
explanation could not explain the
behavior of any other element besides
hydrogen.

What led to quantum


theory?
The visible bands in a
spectra are called the
Balmer series. The UV
and IR lines are called
Lyman and Paschen
series, respectively.
Scientists expected to
see a continuous
spectrum.
This observation of the
hydrogen atom led to
quantum theory.

If electrons behave
as both particles
and waves, where
are they located in
an atom?

Heisenberg Uncertainty
Principle (1927)
It is impossible to determine simultaneously
both
the position and velocity of an electron or
any
other particle.
(p) ( x) = h (Plancks constant)
p = uncertainty in momentum
x = uncertainty in position

The Quantum Model of the Atom

1924 Louis de
Broglie
Electrons should be
considered as waves
confined to the space
around the nucleus.
http://youtube.com/watch?v=x_tNzeouHC4
Bohr applet:
http://www.colorado.edu/physics/2000/quantumzone/bohr.html

Derivation of the de Broglie wavelength


equation
Einstein
Planck
E = mc2
E=h
Therefore:
mc2 = h
[Substitute v (any velocity) for c]
mv2 = h
[rearrange and substitute v for c in c = ; then solve for = v ]

mv2 = hv

Substitute, rearrange, solve for = hv and simplify even further:


mv2

=h
mv

This is the de Broglie wavelength


equation

Germer and Davisson


De Broglies equation was applicable to
any
object, not just atoms. The wave
properties
of electrons were demonstrated in 1927
by
Germer and Davisson (U.S.) using
diffraction by crystals.
This technique is used today in electron
microscopy.

Erwin Schrdinger and the


wave mechanical model

( + + ) + 82m (E-V) = 0
x2 y2 z2
h2
(psi) = wave amplitude function
m = mass of electron
E = energy
V = potential energy
x, y, and z are the coordinates in space where
the equation is solved

Wave functions = orbitals


The solutions to his equation are
known as wave functions and
they describe the regions in space
where there is a high probability of
finding the electron at the point in
space for which the equation was
solved. These regions of space are
called orbitals.

Quantum numbers
Describe the properties of atomic orbitals and the
properties of electrons in these orbitals. There are
4 quantum numbers, the first three of which
result from the solutions to Schrdingers wave
equation.
Principal quantum number (n) the main energy
level occupied by the electron. n= 1,2,3,4, . . .

The total number of orbitals within a given shell is


equal to n2. The total number of electrons within a
given shell is equal to 2n2.

Orbital (or azimuthal) quantum


number (l) or angular momentum
quantum number
Values include l = 0, up to and including n-1
The letter designations originally stood for
sharp,
principal, diffuse and fundamental. These
words were
used to describe different series of spectral
Orbital Letter
Number Number of
lines quantu designati of
electrons
on
orbitals per
emittedm
by
the
elements.
numbe
sublevel
r
0

10

Magnetic and spin quantum


numbers
Magnetic quantum number (ml)
indicates the
orientation of an orbital around the nucleus.
Values range from l to +l (defines how
many of
each type of orbital exists)

Spin quantum number (ms) indicates


the two
possible spin states of electrons in orbitals.

Principal
quantum
number

Orbital
quantum
number

Magnetic quantum
number

Spin quantum numbers


Either clockwise (+ ) or
counterclockwise (- )

n=1

l = 0 (s)

ml = 0

+,

n=2

l = 0 (s),
l = 1 (p)
l = 0 (s),
l = 1 (p),
l = 2 (d)

ml = 0
ml = -1, 0, +1

+,
+ , ; + ,
; + ,

ml = 0
ml = -1, 0, +1
ml = -2, -1, 0, +1, +2

+,
+ , : + , ; +
,
+ , ; + , ;
+ , ; + , ;
+,

l = 0 (s),
l = 1 (p),
l = 2 (d),
l = 3 (f)

ml = 0
ml = -1, 0, +1
ml = -2, -1, 0, +1, +2
ml = -3, -2, -1, 0, +1,
+2, +3

+,
+ , ; + , ; + ,
+ , ; + , ; + , ;
+ , ;
+,
+ , ,; + , ; + , ;
+ , ; + , ; + , ;
+,

n=3

n=4

s
o
r
b
i
t
a
l

p orbitals

d
orbital
s

f orbitals

Electron configuration notation

Long hand configuration (always


start with 1s)
Short hand, or noble gas
configuration (use the noble gas
immediately preceding the element
in question, put its symbol in
brackets [ ], and then write out the
outer shell configuration.
Orbital diagram/notation
configuration

Electron configurationsrules
Aufbau
principle:
An electron
occupies the
lowest energy
orbital that can
receive it.
Diagonal Rule

Order of orbital fillin

Energy in orbital filling

Hunds Rule

orbitals of equal
energy are each
occupied by one
electron before any
orbital is occupied by
a second electron,
and
all electrons in singly
occupied orbitals
must have the same
spin.

Pauli Exclusion principle


no two electrons in the same
atom
have the same set of four
quantum
numbers. The first three may be
the same, but the spin must be
opposite.

Order of orbital filling


http://
intro.chem.okstate.edu/Work
shopFolder/Electronconfnew.
html

Example 1
Boron atomic number 5

Longhand: 1s22s22p1
Shorthand: [He]2s22p1
Orbital diagram:

1s

2s

2p

Example 2
Orbital diagram:

Polonium atomic number 84


Longhand:
1s22s22p63s23p64s23d104p65s24d105p66s24
f145d106p4
Shorthand: [Xe] 6s24f145d106p4

Exceptions to the Aufbau


principle
For Chromium (Cr)
we would predict: 1s2 2s2 2p6 3s2 3p6 4s2
3d4
but it is actually -->1s2 2s2 2p6 3s2 3p6 4s13d5
For Copper (Cu)
we would predict: 1s2 2s2 2p6 3s2 3p6 4s2
3d9
but it is actually --> 1s2 2s2 2p6 3s2 3p6 4s1
3d10

Degenerate orbitals
a group of orbitals with the same
energy
Examples: Chromium (24) Cr
Shorthand: [Ar]4s13d5 NOT [Ar]4s23d4
Mo and W are similar

Copper (29) Cu
Shorthand: [Ar]4s13d10 NOT [Ar]4s23d9
Ag and Au are similar

Additional Definitions
Paramagnetic: An atom has
unpaired
electrons in its electron
configuration.
(Look at its orbital diagram)
Diamagnetic: All electrons in an
atom

Ion Configurations
Electrons will be added to, or taken away
from
orbitals in the following order: s, p, d, f (i.e.
the outer or valence shell first)
Examples:
Cl- 1s22s22p63s23p5 for Chlorine becomes
1s22s22p63s23p6

Na+ 1s22s22p63s1 for sodium becomes


1s22s22p6