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CH101 Lecture 3

The Schrödinger equation can be solved exactly for one-electron systems like hydrogen but requires approximations for multi-electron atoms. While the helium atom involves three centers of charge, its wave function can be approximated using the self-consistent field method. Electron configurations are described using four quantum numbers and follow rules like the Pauli exclusion principle, Aufbau principle, and Hund's rule of maximum multiplicity.

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641 views

CH101 Lecture 3

The Schrödinger equation can be solved exactly for one-electron systems like hydrogen but requires approximations for multi-electron atoms. While the helium atom involves three centers of charge, its wave function can be approximated using the self-consistent field method. Electron configurations are described using four quantum numbers and follow rules like the Pauli exclusion principle, Aufbau principle, and Hund's rule of maximum multiplicity.

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Lecture-III

Schrödinger equation can be solved exactly


for H atom but can be extended for 1-electron
system, like: He+, Li2+ , Be3+ etc…

But for He, there are three centers (2 e and 1


nucleus) gives more complicated picture where
famous three body problem of physics should
be taken into consideration.
To get real solution, approximation of wave
function is necessary, that can be done by
using self-consistent field method (Hartree
Fock Method)
Four Quantum Numbers
‹ Eachelectron in an atom can be
described uniquely by the four
quantum numbers.

‹ Three rules involving quantum numbers


• Pauli Exclusion Principle
• Aufbau Principle
• Hund's Rule
Pauli exclusion principle
‹ no two electrons in an atom can have the
same four quantum numbers. ∴The
maximum number of electrons in any
orbital is two. The maximum number of
electrons in a shell (or subshell) is 2x
the number of orbitals in the shell (or
subshell).
‹ ms = +1/2 or –1/2 (up or down)
Writing electronic
configurations
‹ Electronicconfigurations: a method
of describing the orbital arrangement
of electrons in an atom.

‹ Atomicorbital diagram: pictorially


represents electronic configurations.
Hund’s rule
‹ For degenerate orbitals, lowest
energy is obtained when spin is
maximized. this means…
1. Electrons will fill the subshell
orbitals, one at a time, until each
orbital has one electron.
2. All electrons will have the same spin
(either up or down, or either +1/2 or
–1/2)
3. Only then will electrons be paired.
Electron Filling Pattern
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f 5g
6s 6p 6d 6f 6g 6h
7s 7p

1s 2s 2p 3s 3p 4s 3d 4p 5s

4d 5p 6s 4f 5d 6p 7s
H 1s1
1
Li 1s22s1
3
Na 1s22s22p63s1
11
K 1s22s22p63s23p64s1
19
1s22s22p63s23p64s23d104p65s1
Rb
37
1s22s22p63s23p64s23d104p65s24d10
Cs
55 5p66s1
Fr
87 1s22s22p63s23p64s23d104p65s24d105p66
s24f145d106p67s1
1s2 He 2

Ne
1s22s22p6 10

2 2 6 2 6 Ar
1s 2s 2p 3s 3p 18

1s22s22p63s23p64s23d104p6 Kr
36

1s22s22p63s23p64s23d104p65s24d105p6 Xe
54
1s22s22p63s23p64s23d104p65s24d10 Rn
5p66s24f145d106p6 86
s1 S- block
s2
‹ Alkali metals all end in s1
‹ Alkaline earth metals all end in
s2
‹ really should include He, but it
fits better later.
‹ He has the properties of the
noble gases.
Transition Metals -d block

s1 s1
d1 d2 d3 d5 d5 d6 d7 d8 d10 d10
The P-block p1 p2 p3 p4 p5 p6
F - block
‹ inner transition elements

f1 f2 f3 f4 f5 f6 f7 f8 f9 f10 f11 f12 f13 f14


1
2
3
4
5
6
7

‹ Each row (or period) is the energy


level for s and p orbitals.
‹d orbitals fill up after previous energy
level, so first d is 3d even though it’s in
row 4.
1
2
3d
3
4
5
6
7
1
2
3
4
5
6
7
4f
5f
‹f orbitals start filling at 4f
Writing electron
configurations the easy way

Yes there is a shorthand


Electron Configurations repeat
‹The shape of the periodic table
is a representation of this
repetition.
‹When we get to the end of the
column the outermost energy
level is full.
‹This is the basis for our
shorthand.
The Shorthand
‹ Write symbol of the noble gas
before the element, in [ ].
‹ Then, the rest of the electrons.
‹ Aluminum’s full configuration:
1s22s22p63s23p1
‹ previous noble gas Ne is: 1s22s22p6
‹ so, Al is: [Ne] 3s23p1
More examples
‹Ge = 1s22s22p63s23p64s23d104p2
• Thus, Ge = [Ar] 4s23d104p2
‹Hf =
1s22s22p63s23p64s23d104p65s2
4d105p66s24f145d2
• Thus, Hf = [Xe]6s24f145d2
The Shorthand Again
Sn- 50 electrons
The noble gas
before it is Kr
Takes care of 36
Next 5s2
Then 4d10
Finally 5p2
[ Kr ] 5s2 4d10 5p2
The theory underlying Hund’s rule of maximum
multiplicity

1. Minimization of electron-electron repulsion


- There is less repulsion between electrons in
different orbitals (different regions in space)

Electrons in different orbitals feel a greater Z*,


thus they are more stable
The theory underlying Hund’s rule of
maximum multiplicity

2. Maximization of exchange energy stabilization


- This is a quantum mechanical effect that causes
systems with electrons of the same energy and spin
to be more stable.

- The more exchanges possible, the more stable the


electron configuration of the subshell
For an s-orbital (subshell), the spins must be
different, so no exchanges are possible
For a p subshell, there are different orbitals of the
same energy and exchanges are possible.

Two electrons of opposite spin, no exchange is possible:

Two electrons of the same spin, one exchange is possible:

Initial arrangement

One exchange
Three electrons of same spin, three exchanges are
possible:
Initial arrangement

One exchange

Second exchange

Third exchange

The exchange energy explains why half-filled subshells


are unusually stable.
e.g. the electron configuration of Cr: [Ar]4s1 3d5 instead
of [Ar]4s2 3d4
Πc
energy

pairing
energy
Πe
The IE anomaly at nitrogen and oxygen C

1 Πe

Πc = Coulombic energy
(destabilizing) N

Hypothetical arrangement
3 Πe

Πe = exchange energy
(stabilizing) O

1 Πc + 3 Πe
Exceptions to Electron Filling
‹ There are two exceptions to the
electron filling pattern in the first 40
elements.
• Chromium
• Copper
24
Chromium
Cr

1s2 2s2 2p6 3s2 3p6 4s1 3d5


24 electrons
What is the expected (incorrect) electronic
configuration for chromium?

Why might this exception occur?


29
Cu Copper

1s2 2s2 2p6 3s2 3p6 4s1 3d10


29 electrons
What is the expected (incorrect) electronic
configuration for copper?

Why might this configuration be more stable


than 4s2 3d9?
Term Symbols
Spectroscopists use the word term
to describe the energies involved in
an electronic transition.

2s
hν −1  1 1 
ν = 109,737cm −
 n2 n2 
 1 2
1s Note: this calculation only works
for hydrogen with one electron!
Term Symbols

Term symbols are an abbreviated description


of the energy, angular momentum and spin
of an atom in a particular state.

d-d electronic transitions


hν are responsible for
the color of metal ions.
Term Symbols
Angular Momentum and Spin State

orbitals have different


-2 -1 0 +1 +2 angular momentum values

spin state depends on the


number of unpaired electrons
each spin is -1/2 or +1/2
Term Symbols
Multiplicity (number of spectral lines)
MS
net electrons net spin angular
in same electron momentum
direction spin (S) 2S +1

0 0 1 singlet
1 1/2 2 doublet
2 1 3 triplet
3 3/2 4 quartet
4 2 5 quintet
5 5/2 6 sextet
Term Symbols

Obeying the Pauli Exclusion Principle,


but allowing the d-electrons of a vanadium(III)
ion to occupy any other legal patterns,
how many different patterns could exist and
what would be the magnetic properties
of each pattern?
V3+: 1s2 2s2 2p6 3s2 3p6 3d2

ML = - 2 ML = - 4
Ms = -1 Ms = 0

ML = - 1 ML = 0
Ms = 0 Ms = 0

ML = +1
Some examples Ms = +1
Microstates

How many microstates are possible?

10 × 9
= 45 microstates
1 × 2
Ms
-1 0 +1

+4 1
3F
+3 1 2 1
+2 1 3 1 “triplet F”
+1 2 4 2
ML 0 2 5 2
-1 2 4 2
-2 1 3 1
-3 1 2 1
-4 1
Ms
-1 0 +1

+4 1
3F
+3 1
3P
+2 2
+1 1 3 1 “triplet P”
ML 0 1 4 1
-1 1 3 1
-2 2
-3 1
-4 1
Ms
-1 0 +1

+4 1
3F
+3 1
3P
+2 2
1G
+1 2
ML 0 3 “singlet G”
-1 2
-2 2
-3 1
-4 1
Ms
-1 0 +1

+4
3F
+3
3P
+2 1
1G
+1 1
1D
ML 0 2
-1 1
-2 1
-3
-4
Ms
-1 0 +1

+4
3F
+3
3P
+2 1
1G
+1 1
1D
ML 0 2
-1 1
-2 1
-3
-4

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