11/3/22, 11:32 PM Valence Bond Theory - Chemistry LibreTexts

Valence Bond Theory

Valence bond (VB) theory assumes that all bonds are localized bonds formed between two atoms by the donation of an
electron from each atom. This is actually an invalid assumption because many atoms bond using delocalized electrons. In
molecular oxygen VB theory predict that there are no unpaired electrons. VB theory does a good job of qualitatively
describing the shapes of covalent compounds. While Molecular Orbital (MO) theory is good for understanding bonding in
general. It is more difficult to learn, but predicts the actual properties of molecules better than VB theory. MO theory
actually predicts electron transitions because of the differences in the energy levels of orbitals in the molecule. MO theory
has been more correct in numerous instances and for this reason it is preferred.
Valence Bond theory describes covalent bond formation as well as the electronic structure of molecules. The theory
assumes that electrons occupy atomic orbitals of individual atoms within a molecule, and that the electrons of one atom
are attracted to the nucleus of another atom. This attraction increases as the atoms approach one another until the atoms
reach a minimum distance where the electron density begins to cause repulsion between the two atoms. This electron
density at the minimum distance between the two atoms is where the lowest potential energy is acquired, and it can be
considered to be what holds the two atoms together in a chemical bond.

Topic hierarchy

 d-orbital Hybridization is a Useful  Delocalization of Electrons

Falsehood
For main group molecules, chemists (like Pauling)
thought a long time ago that hypervalence is due to
expanded s²p⁶ octets. The consensus is now clear that d
orbitals are NOT involved in bonding in molecules like
SF₆ any more than they are in SF₄ and SF₂. In all three
cases, there is a small and roughly identical participation
of d-orbitals in the wavefunctions. This has been
established in both MO and VB theory.
To introduce the concept of electron delocalization from
the perspective of molecular orbitals, to understand the
relationship between electron delocalization and
resonance, and to learn the principles of electron
movement used in writing resonance structures in Lewis
notation, known as the curved arrow formalism.

 Hybridization  Hybridization II
Hybridization is the idea that atomic orbitals fuse to
form newly hybridized orbitals, which in turn,
influences molecular geometry and bonding properties.
Hybridization is also an expansion of the valence bond
theory. In order to explore this idea further, we will
utilize three types of hydrocarbon compounds to
illustrate sp , sp , and sp hybridization.
3 2

 Hybrid Orbitals in Carbon Compounds  Overview of Valence Bond Theory

Diamond crystals such as the one shown here are
appreciated by almost everyone, because of their
hardness, sparkle, and high value. They are also
important in many technical applications. However, in
terms of chemistry, diamonds consist of only carbon
atoms, except for impurities. Like diamond, the
chemistry of carbon is indeed very interesting and
valuable.
Valence Bond (VB) Theory looks at the interaction
between atoms to explain chemical bonds. It is one of the
two common theories that helps describe the bonding
between atoms. The other theories is the Molecular
Orbital Theory. Take note that these are theories and
should be treated as such; they are not always perfect.

 Resonance
Resonance structures are used when a single Lewis structure cannot fully describe the bonding; the combination of
possible resonance structures is defined as a resonance hybrid, which represents the overall delocalization of electrons
within the molecule. In general, molecules with multiple resonance structures will be more stable than one with fewer
and some resonance structures contribute more to the stability of the molecule than others - formal charges aid in
d t i i thi
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determining this.

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