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2006-7 Quantum Theory Slides Lecture 3

1) The maximum number of electrons in a subshell depends on the orbital angular momentum quantum number l because l determines the number of sublevels in the subshell, with each sublevel able to hold a maximum of two electrons. 2) Angular momentum plays a key role in atomic spectroscopy. Transitions follow selection rules based on changes in angular momentum, such as Δl = ±1. 3) The Stern-Gerlach experiment provided evidence for space quantization by observing the separation of silver atoms into two distinct spots in a magnetic field, confirming the quantum mechanical predictions over classical expectations.

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91 views20 pages

2006-7 Quantum Theory Slides Lecture 3

1) The maximum number of electrons in a subshell depends on the orbital angular momentum quantum number l because l determines the number of sublevels in the subshell, with each sublevel able to hold a maximum of two electrons. 2) Angular momentum plays a key role in atomic spectroscopy. Transitions follow selection rules based on changes in angular momentum, such as Δl = ±1. 3) The Stern-Gerlach experiment provided evidence for space quantization by observing the separation of silver atoms into two distinct spots in a magnetic field, confirming the quantum mechanical predictions over classical expectations.

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api-19928045
Copyright
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Quantum theory and atomic

spectroscopy
Lecture 3
Angular momentum
The story so far….
• Atoms contain electrons in discrete energy
levels
• The energy levels can be divided into
shells (n) and subshells (l)
• The number of subshells available is
determined by n.
• The maximum number of electrons in a
subshell is given by 2 x (2l + 1)
• Now read on …
Today’s question(s) is (are)……
• Why is the maximum number of electrons in a
subshell dependent on l?
• Why do we call l the orbital angular momentum
quantum number?
Orbital angular momentum

• Because it will “orbit” the nucleus, each electron has an


orbital angular momentum
• In quantum theory, angular momentum is quantised!!
• The direction of the angular momentum vector depends on
whether the electron is moving clockwise or anti-clockwise
• This orbital angular momentum of the electron is given by l
Optical selection rules
• Angular momentum plays
in a role in spectroscopy
• The most common
transitions are called
electric dipole transitions
• The light adds or subtracts
1h/2π (a single quantum)
of angular momentum to
the atom
• Hence there is a selection
rule is ∆l = ± 1
• In hydrogen we have an
extra rule, ∆n ≠ 0
Total orbital angular momentum
• We can add the a.m. of the individual electrons to
get a TOTAL orbital angular momentum for the
atom
• If a subshell is closed (full) the total for that subshell
is 0
• If the subshell is partially filled, we determine its
total angular momentum, usually given the value L,
by a VECTOR sum
• Therefore, when we add two non-zero values of l
we get two or more values of L
Vector addition

• When adding two vectors, we can get more than one


result
• Only discrete values allowed i.e. for orbital angular
momentum, the result must be an integer
• Total is: L = l1 + l2, l1 + l2 – 1,….. (l1 – l2) + 1, l1 – l2
Zeeman effect
• Become a scientist and get
your face on a stamp!
• Zeeman wondered whether
a magnetic field would
affect atomic emission lines
• He had no idea what the
result would be, nor did he
know anything about
quantum numbers!
Zeeman’s experiment

• Looked at light emission as a function of


frequency
• With and without magnetic field
Fabry
FabryPerot
Perot––frequency
frequencyscanner
scanner
(bit
(bitlike
likeaaspectrometer)
spectrometer)
Zeeman’s observation
• The crucial experiment
in cadmium
• The transition splits into
three lines
• The magnitude of the
splitting depends on the
magnetic field
Lorentz’s explanation
• Lorentz “explained” the Zeeman effect in
terms of an electric current in an atom (no
mention of quantised angular momentum
at all)
• Lots of champagne, 1902 Nobel prize for
Hendrick (and Zeeman)!
• Great, so long as you always see three
lines in a magnetic field
• But….. eBz
ν 0 and ν 0 ±
4πme c
Anomalous Zeeman effect
• Thomas Preston had already demonstrated in
1897 that “splittings” could be observed that did
not fit Zeeman’s pattern.
Zeeman effect in helium

• The 2p subshell is in fact into 3 sublevels which have different


energies in a magnetic field.
• New quantum number introduced: ml
• For any l there are (2l + 1) ml sublevels with values
ml = -l, -l + 1,….. l – 1, l Maximum of 2 electrons in each sublevel!
Calculating the Zeeman shift
• The modern form is very similar to Zeeman’s
formula, but for completely different reasons!

ehBz
∆E M L = ML New formula- quantum
4πme c

eB z
Old formula – complete pants!
ν0 and ν0 ±
4πme c
What do these sublevels mean?
• Arnold Sommerfeld
suggested Space
Quantization was the
answer
• Evidence? None!
Enter Stern and Gerlach
• Stern and Gerlach believed space quantization
was literally true
• Set up an experiment to prove it!
Stern – Gerlach experiment
• The interaction between the electron
angular momentum and the magnetic
field depends on their relative
orientations
• Classically, the angular momentum
can point in any direction in the field:
quantum says space quantisation
takes place
• Use the magnetic interaction to move
the atoms in space and look on a
screen
The Stern – Gerlach result
• Classically, expect a diffuse blob! Quantum theory
predicts separate spots
• Using silver atoms, they observed TWO separate
spots: space quantization!!!

1-0
1-0toto
quantum
quantum
theory!
theory!ButBut
there
thereisis
something
something
aabit
bitodd
odd
here….
here….
Answers to the earlier questions..

• Different subshells
hold different numbers
of electrons because
they have different
numbers of sublevels!
• The number of
sublevels is
determined by l
• Each sublevel holds a
maximum of two
electrons
Hang on……

• Why do we see two


spots? We only have an
ODD number of sublevels
for any value of l or L!
• Why can a sublevel hold
just two electrons?

• Next time, we will see that


electron SPIN is the key!

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