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Chem 104A

Review Session

Amlie Nicolay & Michael Boreen


September 21, 2017
On the Physics of Atoms
Know your equations:

Know your quantum numbers:


Principal quantum number n
Angular momentum quantum number l = 0, 1, , n-1
Magnetic quantum number ml = - l, - l + 1, , l
Spin quantum number ms =
Atomic orbitals
Drawing an orbital based on its quantum numbers:
The contour map represents the probability density
The shading represents the sign of the wavefunction

Radial wavefunction Probability density Contour map

Example: 4dxy ?
Radial distribution function; penetration and shielding
Mathematical functions relevant to atomic orbitals:
Radial wavefunction
Probability density
Radial distribution function
4r

Penetration and shielding:


2s orbital has greater penetration
and is better at shielding than 2p
Property of multi-electrons atoms
How to establish the electronic
configuration of an atom?

Example: Titanium? (Z = 22)


Effective nuclear charge and Slaters rule

Example:
3s electron of Na0 and
2p electron of Na+?
Reading term symbols
Know your formulas and the systems quantum numbers:

For a system composed of n electrons, in one or multiple orbitals


Total orbital angular momentum L = l1 + l2 + + ln
Total magnetic quantum number Ml = - L, - L + 1, , L
Total spin quantum number Ms = - S, , S
Total spin angular momentum S = Ms,max
Total angular momentum J = |L + S|,|L + S 1|, |L S|
Finding the ground state

Example:
d4 configuration?
d6 configuration?
Finding excited term symbols from the microstate table

For a p configuration:
Periodic trends
Know the trends in:
Atomic radii
Ionization energies
Electron affinity
Electronegativity (know the
difference between the
Pauling, the Mulliken and the
Allred-Rochow definitions)
Simple Bonding Theory and Symmetry
Hybridization
Hybridization is a simple model
that helps to explain molecular
geometries
In reality, d orbitals are not
usually used in bonding of main-
group compounds (Why?)
Bents Rule
Bents rule (IUPAC Gold Book definition):
In a molecule, smaller bond angles are formed between
electronegative ligands since the central atom, to which the ligands
are attached, tends to direct bonding hybrid orbitals of greater p
character towards its more electronegative substituents.

Example: In CH2F2, are the H-C-H or F-C-F angles larger?


Drawing Lewis Structures
VSEPR
Geometry of central atom is dictated by steric number (SN) =
# of number of bound atoms + # of lone pairs
Determining Structure Using VSEPR
1. Draw Lewis structure show all lone pairs on central atom
2. Determine steric number, and recall corresponding geometry
Steric Number Coordination Number
Methane, ammonia, and water all have SN = 4
Structures based on tetrahedral geometry
Determining Structure Using VSEPR
1. Draw Lewis structure show all lone pairs on central atom
2. Determine steric number, and recall corresponding geometry
3. Fill in atoms and lone pairs based on the following rules for
electron-pair repulsions:
lp-lp repulsions > lp-bp repulsions > bp-bp repulsions
4. Give more space to double bonds than single bonds
5. For SN = 5, Bents rule states that the most electronegative
substituents are in the axial positions
VSEPR Examples
XeF4
36 valence electrons

2 lone pairs
SN = 6

Maximize space between lps

Resulting geometry: square planar


VSEPR Examples
VSEPR Examples
OClF3
34 valence electrons

1 lone pair
SN = 5

Maximize space between lp and bp

Give more space to double bond than single bonds

Resulting geometry: see-saw


VSEPR Examples
Symmetry Operations, Elements
Symmetry Operations, Elements
Point Groups
Great resource for visualizing
symmetry:
http://symmetry.otterbein.edu/
Point Groups
Cubane (C8H8)
Point Group Examples
PPh3 (in conformation shown
below)
Point Group Examples
Ozone (O3)
Do not use single resonance structure

Must use true structure (in this case,


an average of resonance structures)
to get correct point group
Point Group Examples
1,3,5,7-tetrafluoro-1,3,5,7-cyclooctatetraene

F
F

F
F