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TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Basic Assumptions of VSEPR Theory
4. The Valence Shell Electron-pair Repulsion (VSEPR) Model
5. Predicting Molecular Geometries
6. Four or Fewer Valence-Shell Electron Pairs
7. The Effect of Nonbonding Electrons and Multiple Bonds on Bonds Angles
8. Molecules with no central atom
9. Summary
1. Learning Outcomes
Molecules of different substances have diverse shapes. Atoms attach to each other in
various geometric arrangements. The overall molecular shape is determined by its bond
angles in space. The shapes of the molecules can be predicted from their Lewis structures
as prescribed in the model presented in the Valence-Shell Electron-Pair Repulsion
(VSEPR) theory. The base of VSEPR theory was laid down by N.V. Sidgwick and H.M.
Powell in the 1930’s but modern formulation of VSEPR theory was proposed by R.
Nyholm and R.J. Gillespie. VSEPR theory is used for predicting the shapes of individual
molecules based on the extent of interactions of electron pairs in the valence shell of the
atoms. It explains the shape of the molecules having localized electron pairs, bonded or
nonbonded. The shape of a molecule is very important for studying its physical and
chemical properties.
The VESPs are regarded as occupying the localized orbitals with proper orientations in
space so as to minimize the coulombic repulsion between the electron pairs leading to
stable spatial arrangement. The stable spatial arrangements of 2,3,4,5 and 6 electron pairs
with minimum inter-electron repulsion are linear, trigonal planar, tetrahedral, trigonal
bipyramidal and octahedral respectively.
3. Basic Assumptions of the VSEPR Theory
The bond angles in a species depends upon (i) interatomic van der waal repulsion
amongst the nonbonded atoms, (ii) coulombic repulsion due to partial charges on the
atoms due to electronegativity differences, or (iii) repulsion between the electron pairs on
the bonded atoms. Of all the three terms, (iii) i.e. repulsion between the electron pairs on
the bonded atoms, is the most important affecting the geometry of the species. There are
three types of repulsion that take place between the electron pairs of a molecule:
The repulsion between the lone pair (LP) electrons are greater than those between the
bonded pairs (BP). For a stable molecule these repulsions must be minimised. When
repulsion cannot be avoided, the weaker repulsion (i.e. the one that causes the smallest
deviation from the ideal shape) is preferred. The order of the repulsion between various
types of LP is given as:
LP-LP>LP-BP>BP-BP
This is due to the absence of second nucleus at the distal end of the LP. The nucleus at
the either ends of the electron pair tends to polarize the electron cloud in the internuclear
regions. The LP is attracted only its own nucleus tends to occupy larger angular volume
then BP. Further, double bonds occupy more angular space than single bonds. Also
bonding to more electronegative substituent occupies less space than bonding to a less
electronegative substituent. If the central atom belongs to a third or higher period, the
above rules apply for bonding to halogens and oxygen atoms only. For other atoms, the
LP occupies nonbonding s orbitals and bonding is through p orbitals, e.g. in phosphine
(bond angle 94̊) or in arsine (bond angle 92̊).
The valence bond theory and VSEPR theory is usually compared with each other. The
valence bond theory deals with the molecular shape through orbitals that are energetically
accessible for bonding and mainly concerns with the formation of sigma and pi bonds.
Another model named molecular orbital theory also describes that how atoms and
electrons are assembled into molecules and polyatomic ions.
VSEPR theory was structurally accurate and molecular geometries of covalent molecules
have been predicted successfully. VSEPR theory has been criticized for not being
quantitative. The shape of a molecule can be related to following five basic
arrangements.
As discussed earlier, the VSEPR model helps in predicting the molecular structures,
where:
• Atoms are bonded together by electron pairs in valence orbitals
• Since electrons are negatively charged species they tend to repel other electrons
present as lone pairs
• Bonding pairs of shared electrons tend to repel other bonding pairs of electrons in
the valence orbital
The factors that affect the geometry of the molecular species are (i) the total number of
electron pairs in the valence shell of the central atom, (ii) availability of the low energy
orbitals and (iii) lone pairs. The LPs are assigned the positions where LP-LP repulsions
are minimum and LP can expand more readily due to the larger angular volume. The
table below summarizes the shapes of molecules predicted from VSEPR theory.
Here are some examples of species where d orbitals are not used: Isoelectronic CH4,
NH3, H2O, HF and NH4+ in all of these the central atom uses sp3 hybrid orbitals. In CH4,
all the orbitals have BPs resulting in a symmetrical structure with bond angle 109.5̊. NH3,
H2O and HF have 1, 2, 3 LPs respectively. The increasing LP-LP repulsion decreases the
bond angles from 109.5̊ to 107̊ in NH3 and to 104̊ in H2O as shown in figure .1
Figure 1: The structure of methane (CH4), ammonia (NH3), water (H2O), hydrogen fluoride and
ammonium ion (NH4+) from valence shell electron pair repulsion theory (VESPRT)
When a proton gets attach to the LP of NH3 and forms NH4+ ion, the LP gets polarized by
the positive charge of the proton and gets concentrated along the N-H axis. Due to the
decreased electron density around nitrogen atoms, the three BPs open up, and as all the
four electrons pairs are now BPs, a symmetrical tetrahedral structure with bond angle
109.5̊ results. The positive charge of the proton is equally shared by all the four protons.
Now, let us discuss about the geometry of species which involve d orbitals. Let us
consider the species PF5, SF4, ClF3, and [ICl2]- , having 10 electrons each in the valence
shell of the central atom. The LPs present on P, S, Cl and I are 0, 1, 2, and 3 respectively.
The 10 electrons are housed in trigonal bipyramidal geometry ie in sp3d hybrid orbitals.
See figure 2
Figure 2: Possible geometries of (a) Phosphorus Pentachloride PF5, (b) Sulphur tetrafluoride SF4, (c)
Chloride trifluoride ClF3, and (d) Dichloriodate (I) ion ICl2- ; on the basis of VSEPR theory
Compounds with highly electronegative fluorine which creates partial positive charge on
the central atom and reducing the size of the d orbitals.
Role of outer d orbitals: In the compounds like nitronium (NO2+) ion, nitrite (NO2 -) ion
the splitting of d orbitals should take place. This depends upon the energy of d orbitals
and their diffused nature. Outer d electrons are used only in the case of
• Formation of large number of bonds (5, 6,or even 7)
• Compounds with highly electronegative fluorine which creates partial positive
charge on the central atom and reducing the size of the d orbitals
Figure 3: The VSEPR pictures of nitroniumion NO2+ (a), nitrite ion NO2- (b), and the free radical
NO2 (c)
For determination of geometry of the molecule with the help of VSEPR model various
steps involved are:
1. Write down the Lewis dot structure of the molecule
2. Count and arrange the total number of electron pairs around the central atom. The
arrangement should be done in such a way so that valence shell electron pair repulsion
can be minimized.
3. Describing the molecular geometry in terms of the angular arrangement of the bonding
pairs
Which contains:
The ammonia has distorted tetrahedral geometry because in this arrangement the
electron pair repulsion between these four electron pairs is minimum.
• This arrangement is for the valence electron pairs. What about the atoms in a
compound?
• The molecular geometry is the location of the atoms of a compound in space
• We can predict the molecular geometry from the electron pair geometry
Here we’ll try to understand some molecules or ions, which obey the octet rule:
Example:
Using the VSEPR model we can predict the geometries of a) SnCl3 - and b) O3
When the central atom has‘d’ orbitals available, then it may have more than 4 electron
pairs around it. Such central atoms exhibit a variety of molecular geometries:
The trigonal bipyramidal arrangement for atoms with 5 pairs of valence electrons
contains two geometrically distinct types of electron pairs, axial and equitorial:
The octahedral structure contains 6 pairs of valence electrons. All positions are
equivalent and at 90°from other electron pairs.
If there is one nonbonding pair of electrons, it makes no difference where we place them.
However, if there are two nonbonding pairs of electrons, the second pair will be
180° from the first to minimize steric interactions
• The first carbon has four pairs of valence electrons and will be tetrahedral
• The second carbon has three (multiple bonds count as one in VSEPR) and will be
trigonal Planar
• The oxygen on the right has four and will be tetrahedral (only has two bonds
pairs and thus it will appear as a "bent" conformation)
9. Limitations of VSEPR theory
Though satisfactory for many species, the VSEPR theory fails for most of the 14 electron
systems. For IF7 and ReF7 (where no LP exists) the expected structure is pentagonal
bipyramidal with sp3d3 hybridization. It fails to explain the species with LPs. Thus it
doesn’t give a correct structure for XeF6 or SbF63- (distorted octahedron in which the LP
is trying to emerge out of the triangular phase; IF6- (lower symmetry octahedron); Pb(II),
As(III) and Sb(III) complexes with hexadentate ligands (pentagonal bipyramid, where the
LP seems to occupy the axial orbital so that it appears that in these complexes, the LP
occupies less space than the BPs). Further, though the alkaline earth halides are ionic in a
solid state, they are covalent in the vapour phase, where some of them have a bent V-
shape. This cannot be explained as the alkaline earth ions, after the formation of the
dihalides, do not have any electron pair on them. Generally it fails to predict the shapes
of isoelectronic species and transition metal compounds. This model does not take
relative sizes of substituents and stereochemically inactive lone pairs into account. See
figure. 3
Figure 3: Structure of XeF6 and SbF3 in which the lone pair of electrons is emerging out of the
triangular face
10. Summary