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VSEPR: Valence Shell Electron Pair Repulsion Theory

Predicts an approximate shape/geometry of a given Lewis structure


Assume that each bond (single or multiple) and each lone pair on a central atom
occupies a region of space; the bonds and lone pairs are arranged in such a way about
the central atom so as to minimize repulsions among them.

bonds +
2 3 4 5 6
lone pairs
trigonal trigonal
linear tetrahedral octahedral
planar bipyramidal
O O O O
arrangement O O O
O O O O O O
O O O O O O
O O O O
O O

Some of the corners of the arrangement may be taken up by lone pairs on the central
atom. This will determine the actual molecular geometry, defined by the atom positions.
Each combination of bonds and lone pairs can be represented by AXnEm with A =
central atom, X = atoms bound to A, E = lone pair on A.
lone pairs Advantages
BP + LP
0 1 2 3 based on a simple,
AX2: linear qualitative premise
2
O C O fast and intuitive
AX3: trigonal planar AX2E: bent qualitatively accurate
F especially useful for
3 N organic compounds
B O Cl
F F
Disadvantages
AX4: tetrahedral AX3E: pyramidal AX2E2: bent
requires a valid Lewis
H H structure, so cannot be
4 H N
H C H O used if Lewis isnt valid
H H H
H no TM complexes
AX5: trigonal AX3E2: AX2E3: no odd-e molecules
AX4E: see-saw many structures not
bipyramidal T-shaped linear
correctly predicted by
F F F F
5 F F Lewis model
F P S F Cl Xe offers only qualitative,
F F approximate predict-
F F F F
ions for non-symmetric
AX5E: square AX4E2: molecules
AX6: octahedral
pyramidal square planar
the simple premise is
F F an oversimplification of
6 F F F F
S F F Xe the underlying physical
F F I F F principles
F F F
How to Determine a VSEPR Structure
1) Draw the Lewis Structure
2) Count the bonds and lone pairs about the central atom
(note that multiple bonds are one region of electron density)
3) Determine the electron pair arrangement (both bond pairs and lone pairs)
4) Position the atoms and lone pairs so as to minimize lone pair repulsions
5) Name the molecular geometry based on the position of the atoms

Examples
180
AX2: linear arrangement
BeF2 linear geometry
F Be F

F
120 AX3: trigonal planar arrangement
BF3 B trigonal planar geometry
F F

H
109.5
AX4: tetrahedral arrangement
CH4 H C H tetrahedral geometry
H

90
F
F AX5: trigonal bipyramidal arrangement
PF5 F P trigonal bipyramidal geometry
120 F
F

F
F F AX6: octahedral arrangement
SF6 S
F F octahedral geometry
F 90

O
N AX3, regardless of resonance:
O O trigonal planar
NO3 O O multiple bonds count as a single density region!
N N resonance forms do not affect VSEPR!
O O O O

All AXn molecules have identical electron pair arrangement and molecular geometry!
More Examples
H
109.5
AX4: tetrahedral arrangement
CH4
H C H tetrahedral geometry
H
AX3E: tetrahedral arrangement
H N H
NH3 trigonal pyramidal geometry
H One corner is a lone pair!

AX2E2: tetrahedral arrangement


H O
H2O bent geometry
H Two corners are lone pairs!

90
F
F AX5: trigonal bipyramidal arrangement
PF5 F P trigonal bipyramidal geometry
120 F
F

F
AX4E: trigonal bipyramidal arrangement
F see-saw geometry
SF4 S
F First LP: equatorial
F

F
AX3E2: trigonal bipyramidal arrangement
ClF3 F Cl T-shape geometry
Second LP: also equatorial
F

F
AX2E3: trigonal bipyramidal arrangement
XeF2 Xe linear geometry
All LP equatorial in trigonal bipyramidal!
F

Which corners do the lone pairs occupy?


1) tighter angle = more repulsion: 90 > 120 > 180
less repulsion
2) lone pairs need more room than bond pairs:
interaction: LP-LP > LP-BP > BP-BP
less repulsion
LPs occupy positions that give greatest LP-LP and LP-BP angles