Molecular geometry

• Molecular geometry: is the three-dimensional

arrangement of the atoms that constitute a
molecule.

• It includes the general shape of the molecule

as well as bond lengths, bond angles,
torsional angles and any other geometrical
parameters that determine the position of
each atom.
• Molecular geometry influences several properties of
a substance including its reactivity, polarity,
phase of matter, color, magnetism and biological
activity.

• The angles between bonds that an atom forms

depend only weakly on the rest of molecule.
• Molecules, by definition, are most often held
together with covalent bonds involving single,
double, and/or triple bonds, where a "bond" is a
shared pair of electrons (the other method of
bonding between atoms is called ionic bonding and
involves a positive cation and a negative anion).

• Molecular geometries can be specified in terms of

bond lengths, bond angles and torsional angles.
• The bond length: is defined to be the average
distance between the nuclei of two atoms bonded
together in any given molecule.
• A bond angle: is the angle formed between three
atoms across at least two bonds.
• Molecular geometry is determined by the
quantum mechanical behavior of the electrons.
Using the valence bond approximation this can
be understood by the type of bonds between the
atoms that make up the molecule.
• When atoms interact to form a chemical bond,
the atomic orbitals of each atom are said to
combine in a process called orbital hybridisation.
• Electron Geometry vs Molecular Geometry
• Molecular geometry is described as the 3D arrangement of
atoms in a molecule, normally relative to a single central
atom.
• Whereas, electron geometry is the 3D arrangement of
electron pairs around a central atom, whether bonding or
non-bonding.
• A lone (non-bonding) pair refers to a pair of valence
electrons that are not shared with another atom in a
covalent bond. And a bond pair is a pair of electrons in a
bond.
• These arrangements are illustrated below with
balloons and models of molecules for each.
• Determination of molecular geometry
• Several methods have developed to determine
the distance between the various atoms in a
molecule and also the angle in the bond
involved. However, the geometries and
observed shape of the covalent molecules can
be predicted theoretically with the help of
valence shell electron pair repulsion theory
(VSEPR theory).
 The VSEPR model
• The valence shell electron pair repulsion
model assumes that electron pairs repel one
another.
• This produces a set of molecular geometries
which depend only on the number of valence
shell electron pairs and not on the nature of
the atoms present.
 VSEPR theory
The main features of VSEPR theory are:
• The shape of a molecule depends upon the number of valence shell
electron pairs (bonded or non-bonded) around the central atom.
• Pairs of electrons in the valence shell repel one another since their
electron clouds are negatively charged.
• The positions of the electron pairs in space around the central atom
are such that they minimize repulsion and thus maximize distance
between them.
• These repulsive forces alter the bond angles of the molecule or ion.
• The electronic repulsion between two pairs of electrons will be
minimum if they are as far apart as possible. On this basis, the
following geometrical arrangements are most suited.
• It is well known that the electron pairs, being
negatively charged, repel each other. This repulsion
causes the electron pairs around the central atom to
arrange as far apart from each other as possible. This
minimizes the repulsion.
• Under the influence of a single nucleus, a lone pair offers more repulsion
than a bond pair which is influenced by two nuclei. This causes a slight
decrease in bond angles (angles between bonds or bond pairs).
• If all of the electron groups are bond pairs (no lone pairs), the molecular
geometry and electron geometry are the same. An example is a methane
molecule, CH4 with 4 bond pairs and no lone pairs, all 4 of carbon’s
valence electrons are bonded with hydrogen atoms. Its molecular, as
well as electronic geometry, is tetrahedral.
• An example with differing molecular and electron geometries is that of
ammonia, NH3. With the central atom nitrogen having 5 valence
electrons, it possesses 3 bond pairs and a lone pair of electrons. Its
molecular geometry is trigonal pyramidal while its electron geometry is
tetrahedral.
 Types of molecular structure
• A bond angle is the geometric angle between two adjacent
bonds. Some common shapes of simple molecules include:
• Linear: In a linear model, atoms are connected in a
straight line. The bond angles are set at 180°. Ex: carbon
dioxide and nitric oxide have a linear molecular shape.

• Trigonal planar: Molecules with the trigonal planar shape

are somewhat triangular and in one plane (flat).
Consequently, the bond angles are set at 120°. For
example, boron trifluoride.
• (iii) Tetrahedral molecular geometry:
• In a tetrahedral molecular geometry, a central atom is located at the center with four substituents
that are located at the corners of a tetrahedron.
• The bond angle of the structure 109028’.
• Example: CH4, CCl4 etc.
• (iv) Trigonal Bipyramidal molecular geometry:
• Let’s take an example of PF5. Here, repulsion can be minimized by even distribution of electrons
towards the corner of a trigonal pyramid. In a trigonal bipyramid, three positions lie along the
equator of the molecule. The two positions lie along an axis perpendicular to the equatorial plane.
• The bond angle are 900 and 1200
• (v) Octahedral molecular geometry:
• Octahedral molecular geometry describes the shape of compounds with six atoms or groups of
atoms or ligands symmetrically arranged around a central atom, defining the vertices of an
octahedron.
• The bond angle is 900.
• Example: SF6, TeF6 etc.