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Definition of Hybridization

Hybridization happens when atomic orbitals mix to form new atomic orbitals. The new orbitals have the same
total electron capacity as the old ones. The properties and energies of the new, hybridized orbitals are an 'average'
of the original unhybridized orbitals.
The concept of hybridization was introduced because it was the best explanation for the fact that all of the C - H
bonds in molecules like methane were identical.

Example
Carbon atoms naturally have electron configuration 1s2 2s2 2p2.
The four outermost electrons, i.e. those in the 2s and 2p sublevels are available to form chemical bonds with other
atoms.
The 2s orbital is capable of holding up to two electrons, and there are three 2p orbitals, each capable of holding up to
two electrons, which means the 2p orbitals can hold up to six electrons.
Individually, these electron orbitals look something like this. (Each is centered on carbon's nucleus and the p orbitals
make angles of 90 with one another.)

The 2s orbital and the three 2p orbitals hybridize to form a new hybrid orbital, called sp3, which is capable of holding
up to eight electrons.
The sp3 hybrid orbital, which is the sum of the original 2s and 2p orbitals, looks something like this:

sp3 hybrid orbitals have a tetrahedral shape - each orbital makes an angle of 109.5 with the others. This angle
maximizes the distance between the orbitals, which is natural given that the electrons in each orbital repel one
another.
The shape of molecules like methane, CH4, with bond angles of 109.5, is consistent with sp3 hybridization of carbon
atoms.

Here is an energy level diagram showing how electron energies change in hybridization.

Orbital hybridisation
From Wikipedia, the free encyclopedia

Four sp3 orbitals.

Three sp2 orbitals.

In chemistry, hybridisation (or hybridization) is the concept of mixing atomic orbitals into new hybrid
orbitals (with different energies, shapes, etc., than the actual orbitals hybridising) suitable for the pairing of
electrons to form chemical bonds in valence bond theory. Hybrid orbitals are very useful in the explanation
of molecular geometry and atomic bonding properties. Although sometimes taught together with the valence
shell electron-pair repulsion (VSEPR) theory, valence bond and hybridisation are in fact not related to the
VSEPR model.[1]

Contents
[hide]

1 Historical development

2 spx and sdx terminology

3 Types of hybridisation

3.1 sp3 hybrids

3.2 sp2 hybrids

3.3 sp hybrids

4 Hybridisation and molecule shape

4.1 Main group compounds with lone pairs

5 Hybridisation of hypervalent molecules

5.1 Traditional description

5.2 Coulson-Fischer description

5.2.1 Main group compounds with lone pairs

5.2.2 Pi bonding

6 Clarifying misconceptions

6.1 VSEPR electron domains and hybrid orbitals are different

6.2 Non-inclusion of d orbitals in main group compounds

6.3 Non-inclusion of p orbitals in transition metal complexes

7 Hybridisation theory vs. MO theory

8 See also

9 References

10 External links

Historical development[edit]
Chemist Linus Pauling first developed the hybridisation theory in order to explain the structure
of molecules such as methane (CH4).[2] This concept was developed for such simple chemical systems, but the
approach was later applied more widely, and today it is considered an effective heuristic for rationalizing the
structures oforganic compounds.
Orbitals are a model representation of the behaviour of electrons within molecules. In the case of simple
hybridisation, this approximation is based on atomic orbitals, similar to those obtained for the hydrogen atom,
the only atom for which an exact analytic solution to its Schrdinger equation is known. In heavier atoms, like
carbon, nitrogen, and oxygen, the atomic orbitals used are the 2s and 2p orbitals, similar to excited state
orbitals for hydrogen. Hybrid orbitals are assumed to be mixtures of these atomic orbitals, superimposed on
each other in various proportions. It provides a quantum mechanical insight to Lewis structures. Hybridisation
theory finds its use mainly in organic chemistry.

spx and sdx terminology[edit]


This terminology describes the weight of the respective components of a hybrid orbital. For example, in
methane, the C hybrid orbital which forms eachcarbonhydrogen bond consists of 25% s character and 75% p
character and is thus described as sp3 (read as s-p-three) hybridised. Quantum mechanics describes this
hybrid as an sp3 wavefunction of the form N(s + 3p), where N is a normalization constant (here 1/2) and p
is a p orbital directed along the C-H axis to form asigma bond. The ratio of coefficients (denoted in general)
is 3 in this example. Since the electron density associated with an orbital is proportional to the square of the
wavefunction, the ratio of p-character to s-character is 2 = 3. The p character or the weight of the p component
is N22 = 3/4.
For atoms forming equivalent hybrids with no lone pairs, there is a correspondence to the number and type of
orbitals used. For example, sp3 hybrids are formed from one s and three p orbitals. However, in all other cases,
there is no such correspondence. The two bond-forming hybrid orbitals of oxygen in water can be described as
sp4, which means that they have 20% s character and 80% p character, but does not imply that they are formed
from one s and four p orbitals. As a result, the amount of p-character is not restricted to integer values; i.e.,
hybridisations like sp2.5 are also readily described.

In general, any two hybrid orbitals on the same atom must be mutually orthogonal. For an atom with s and p
orbitals forming hybrids hi and hj with included angle
relation:

, the orthogonality condition implies the

. The p-to-s ratio for hybrid i is

, and for hybrid j it is

. The bond

directed towards a moreelectronegative substituent tends to have higher p-character as stated in Bent's rule. In
the special case of equivalent hybrids on the same atom, again with included angle
just

, the equation reduces to

. For example, BH3 has a trigonal planar geometry, three 120 bond angles, three

equivalent hybrids about the boron atom, and thus

becomes

for the p-to-s ratio. In other words, sp2 hybrids.

giving

An analogous notation is used to describe sdx hybrids. For example, the permanganate ion (MnO4-) has
sd3 hybridisation with orbitals that are 25% s and 75% d.

Types of hybridisation[edit]
sp3 hybrids[edit]
Hybridisation describes the bonding atoms from an atom's point of view. That is, for a tetrahedrally coordinated
carbon (e.g., methane CH4), the carbon should have 4 orbitals with the correct symmetry to bond to the 4
hydrogen atoms.
Carbon's ground state configuration is 1s2 2s2 2px1 2py1 or more easily read:

1s

2s

2px

2py

C
2pz

The carbon atom can utilize its two singly occupied p-type orbitals (the designations p x py or pz are meaningless
at this point, as they do not fill in any particular order), to form two covalent bonds with two hydrogen atoms,
yielding the "free radical" methylene CH2, the simplest of the carbenes. The carbon atom can also bond to four
hydrogen atoms by an excitation of an electron from the doubly occupied 2s orbital to the empty 2p orbital, so
that there are four singly occupied orbitals.

1s

2s

2px

2py

2pz

C*

As the additional bond energy more than compensates for the excitation, the formation of four C-H bonds is
energetically favoured.

Quantum mechanically, the lowest energy is obtained if the four bonds are equivalent which requires that they
be formed from equivalent orbitals on the carbon. To achieve this equivalence, the angular distributions of the
orbitals change via a linear combination of the valence-shell (Core orbitals are almost never involved in
bonding) s and p wave functions[3] to form four sp3 hybrids.

1s

sp3

sp3

sp3

sp3

C*

In CH4, four sp3 hybrid orbitals are overlapped by hydrogen's 1s orbital, yielding four (sigma) bonds (that is,
four single covalent bonds) of the same length and strength.

translates into

sp2 hybrids[edit]

Ethene structure

Other carbon based compounds and other molecules may be explained in a similar way as methane. Take, for
example, ethene (C2H4). Ethene has a double bond between the carbons.
For this molecule, carbon will sp2 hybridise, because one (pi) bond is required for the double bond between
the carbons, and only three bonds are formed per carbon atom. In sp2 hybridisation the 2s orbital is mixed
with only two of the three available 2p orbitals:
C*

1s

sp2

sp2

sp2

2p

forming a total of three sp2 orbitals with one p orbital remaining. In ethylene (ethene) the two carbon atoms form
a bond by overlapping two sp2 orbitals and each carbon atom forms two covalent bonds with hydrogen by s
sp2 overlap all with 120 angles. The bond between the carbon atoms perpendicular to the molecular plane is
formed by 2p2p overlap. The hydrogencarbon bonds are all of equal strength and length, which agrees with
experimental data.

sp hybrids[edit]

A schematic presentation of hybrid orbitals sp

The chemical bonding in compounds such as alkynes with triple bonds is explained by sp hybridisation.

1s

sp

sp

2p

2p

C*

In this model, the 2s orbital mixes with only one of the three p orbitals resulting in two sp orbitals and two
remaining unchanged p orbitals. The chemical bonding in acetylene (ethyne) (C2H2) consists of spsp overlap
between the two carbon atoms forming a bond and two additional bonds formed by pp overlap. Each
carbon also bonds to hydrogen in a ssp overlap at 180 angles.

Hybridisation and molecule shape[edit]


Hybridisation helps to explain molecule shape:

Classification

Main group

Transition metal[4]

AX2

Linear (180)

Bent (90)

sp hybridisation

sd hybridisation

E.g., CO2

E.g., VO2+

Trigonal planar (120)

Trigonal pyramidal (90)

sp2 hybridisation

sd2 hybridisation

E.g., BCl3

E.g., CrO3

Tetrahedral (109.5)

sp3 hybridisation

sd3 hybridisation

E.g., CCl4

E.g., MnO4

Square pyramidal (66, 114)[5]

sd4 hybridisation

E.g., Ta(CH3)5

Trigonal prismatic (63, 117)[5]

sd5 hybridisation

E.g., W(CH3)6

AX3

AX4

AX5

AX6

Main group compounds with lone pairs[edit]


For main group compounds with lone electron pairs, the s orbital lone pair (analogous to s-p mixing
in molecular orbital theory) can be hybridised to a certain extent with the bond pairs [6] to maximize energetic
stability according to its Walsh diagram. This rationalisation is applied to explain deviations in ideal bond angles
(i.e. only p orbitals used for bonding), most commonly in second and third period elements.

Trigonal pyramidal (AX3E1)

s-orbital can be hybridised with the three p-orbital bonds to give bond angles greater than 90.

E.g., NH3

Bent (AX2E1-2)

s-orbital lone pair can be hybridised with the two p-orbital bonds to give bond angles greater
than 90. The out-of-plane p-orbital can either be a lone pair or pi bond. If it is a lone pair, it results in
inequivalent lone pairs contrary to the common picture depicted by VSEPR theory (see below).

E.g., SO2, H2O


Monocoordinate (AX1E1-3)

s-orbital lone pair can be hybridised with the p-orbital bond. The two out-of-line p-orbitals can
either be lone pairs or pi bonds. The p-orbital lone pairs are inequivalent from the s-rich lone pair.

E.g., CO, SO, HF

Hybridisation of hypervalent molecules[edit]


Traditional description[edit]
In general chemistry courses and mainstream textbooks, hybridisation is often presented for main group AX5
and above, as well as for transition metal complexes, using the hybridisation scheme first proposed by Pauling.

Classification

AX2

AX3

Main group

Transition metal

Linear (180)

sp hybridisation

E.g., Ag(NH3)2+

Trigonal planar (120)

AX4

sp2 hybridisation

E.g., Cu(CN)32

Square planar (90)

sp2d hybridisation

E.g., PtCl42

Trigonal bipyramidal (90, 120)

sp3d hybridisation

E.g., PCl5, Fe(CO)5

Octahedral (90)

sp3d2 hybridisation

E.g., SF6, Mo(CO)6

Pentagonal bipyramidal (90, 72)

sp3d3 hybridisation

E.g., IF7, V(CN)74

Square antiprismatic

sp3d4 hybridisation

E.g., IF8, Re(CN)83

AX5

AX6

AX7

AX8

AX9

Tricapped trigonal prismatic

sp3d5 hybridisation

E.g., ReH92

However, such a scheme is now superseded as more recent calculations based on molecular orbital theory
have shown that in main-group molecules the d component is insignificant, while in transition metal complexes
the p component is insignificant (see below).

Coulson-Fischer description[edit]
In the Coulson-Fischer description, the singly-occupied bond orbitals utilize a ligand orbital component to
account for the ionicity of the bond.[7] As shown by computational chemistry, hypervalent molecules can only be
stable given strongly polar (and weakened) bonds with electronegative ligands such as fluorine or oxygen to
reduce the valence electron occupancy of the central atom to below 8 (or 12 for transition metals). The added
ligand orbital component, which translates to ionic character, also allows the central atom to form more orbitals
for bonding than would be possible with non-polar covalent bonds. This orbital picture can be illustrated in
Lewis structures by ionic-covalent resonance.

Classification

AX2

AX3

AX4

Main group

Transition metal[4]

Linear (180)

A(s)+X()

E.g., Ag(NH3)2+

Trigonal planar (120)

A(s)+X()

E.g., Cu(CN)32

Square planar (90)

A(sd)+X()

E.g., PtCl42

Trigonal bipyramidal (90, 120)

A(sp3)+X()

A(sd)+X()

E.g., PCl5

E.g., Fe(CO)5

Octahedral (90)

A(sp3)+X()

A(sd2)+X()

E.g., SF6

E.g., Mo(CO)6

Pentagonal bipyramidal (90, 72)

A(sp3)+X()

A(sd3)+X()

E.g., IF7

E.g., V(CN)74[8]

Square antiprismatic

A(sp3)+X()

A(sd4)+X()

E.g., IF8[9]

E.g., Re(CN)83[10]

Tricapped trigonal prismatic

A(sd5)+X()

E.g., ReH92

AX5

AX6

AX7

AX8

AX9

Main group compounds with lone pairs[edit]

For hypervalent main group compounds with lone electron pairs, the bonding scheme can be split into two
components: the "hypervalent bonding" component and the "regular bonding" component. The "regular
bonding" component has the same description (see above), while the "hypervalent bonding" component
consists of A(p)+X() hybrids. The table below shows how each shape is related to the two components and
their respective descriptions.

Regular bonding component

Bent

Hypervalent
bonding
component
(A(p)+X())

Seesaw (AX4

Monocoordinate

E1) (90, 180,

Pentagonal
planar
equator

E.g., SF4

+ p-orbital

E.g., ClF3

Square

lone pair

E.g., XeF2

Square
planar (AX4E2) (90)

pyramidal (AX5E1)
-

(90, 90)

E.g., ClF5

Pentagonal

+ two p-orbital
lone pairs, s-orbital

lone pair

Linear (AX2E3)
(180)

X3E2) (90, 180)

>90)

Linear axis

Square
planar
equator

T-shaped (A

+ p-orbital lone
pair, s-orbital lone
pair

E.g., XeF4

Pentagonal

pyramidal (AX6E1)

planar (AX5E2) (72)

(90, 72)

E.g., XeOF5

+ p-orbital lone
pair, s-orbital lone
pair

E.g., XeF5

Pi bonding[edit]
Hypervalent pi bonding in the Coulson-Fischer description is also explained analogously using A(p )+X(p) or
A(d)+X(p) hybrids. For example, in ozone, the central oxygen's orbital hybridises with the two surrounding
oxygen orbitals and overlaps with them to form two polar pi bonds with bond order of 0.5 each.

Clarifying misconceptions[edit]
VSEPR electron domains and hybrid orbitals are different[edit]
The simplistic picture of hybridisation taught in conjunction with VSEPR theory does not agree with high-level
theoretical calculations[6] despite its widespread usage in many textbooks. For example, following the
guidelines of VSEPR, the hybridization of the oxygen in water is described as sp 3 with two lone electron-pairs
and two bonds in four equal-energy, symmetrical orbitals making a tetrahedron. [11] However, molecular
orbital calculations give orbitals which reflect the symmetry of the molecule. [12] One of the two lone pairs is in a
pure p-type orbital, with its electron density perpendicular to the H-O-H framework. [12] The other lone pair is in
an approximately sp0.8 orbital that is in the same plane as the H-O-H bonding.[12] Photoelectron spectra confirm
the presence of two different energies for the nonbonded electrons. [13]
In contrast, the orbitals used to make the O-H bonds are approximately sp 4 hybrids.[14] It has been argued that it
is this change in the mixing of the orbitals that is responsible for the compression of the H-O-H angle down to
the experimental 104.5 degrees, not some change in the repulsion of electrons.[14] Thus while VSEPR and its
application to hybridisation predicts the correct atomic framework for water and other molecules with lone
electron pairs, it may do so for the wrong reason.

Non-inclusion of d orbitals in main group compounds[edit]


Main article: Hypervalent molecule
In 1990, Magnusson published a seminal work definitively excluding the role of d-orbital hybridization in
bonding in hypervalent compounds of second-row elements. This had long been a point of contention and
confusion in describing these molecules using molecular orbital theory. Part of the confusion here originates
from the fact that one must include d-functions in the basis sets used to describe these compounds (or else
unreasonably high energies and distorted geometries result), and the contribution of the d-function to the
molecular wavefunction is large. These facts were historically interpreted to mean that d-orbitals must be

involved in bonding. However, Magnusson concludes in his work that d-orbital involvement is not implicated in
hypervalency.[15]

Non-inclusion of p orbitals in transition metal complexes[edit]


Similarly, p orbitals have long been thought to be utilized by transition metal centers in bonding with ligands,
hence the 18-electron description; however, recentmolecular orbital calculations have found that p orbitals do
not contribute significantly to the hybrid orbitals in transition metal complexes, [16] even though the contribution of
the p-function to the molecular wavefunction is calculated to be somewhat larger than that of the d-function in
main group compounds.

Hybridisation theory vs. MO theory[edit]


Hybridisation theory is an integral part of organic chemistry and in general discussed together with molecular
orbital theory in advanced organic chemistry textbooks although for different reasons. One textbook notes that
for drawing reaction mechanisms sometimes a classical bonding picture is needed with two atoms sharing two
electrons.[17] It also comments that predicting bond angles in methane with MO theory is not straightforward.
Another textbook treats hybridisation theory when explaining bonding in alkenes [18] and a third[19] uses MO
theory to explain bonding in hydrogen but hybridisation theory for methane.
Bonding orbitals formed from hybrid atomic orbitals may be considered as localized molecular orbitals, which
can be formed from the delocalized orbitals of molecular orbital theory by an appropriate mathematical
transformation. For molecules with a closed electron shell in the ground state, this transformation of the orbitals
leaves the total many-electron wave function unchanged. The hybrid orbital description of the ground state is
therefore equivalent to the delocalized orbital description for explaining the ground state total energy and
electron density, as well as the molecular geometry which corresponds to the minimum value of the total
energy.
There is no such equivalence, however, for ionized or excited states with open electron shells. Hybrid orbitals
cannot therefore be used to interpret photoelectron spectra, which measure the energies of ionized states,
identified with delocalized orbital energies using Koopmans' theorem. Nor can they be used to interpret UVvisible spectra which correspond to electronic transitions between delocalized orbitals. From a pedagogical
perspective, hybridisation approach tends to over-emphasize localisation of bonding electrons and does not
effectively embrace molecular symmetry as does MO theory.

Introduction
Based on Valence Bond Theory, carbon would only be able to form two covalent bonds, making
CH2. However, as you will find out, we know that this is not true and that in reality, it makes
CH4. The hybridization of orbitals is also greatly favored because hybridized orbitals are lower in
energy compared to their separated, unhybridized counterparts. This results in more stable
compounds when hybridizationoccurs. Also, major parts of the hybridized orbitals, or the frontal
lobes, overlap better than the lobes of unhybridized orbitals. This leads to better bonding.
Carbon is a perfect example showing the need for hybrid orbitals. As you know, Carbon's ground
state configuration is:

According to the valence bond theory, carbon should form two covalent bonds, resulting in a
CH2. However, tests show that CH2 is highly reactive and cannot exist outside of a reaction.
Therefore, this does not explain how CH 4 can exist. However, you can excite a 2s electron and
bump it into one of the 2p orbitals. This would give you the following configuration:

While this would allow us to have four covalent bonds, resulting in CH 4, it also implies that the
C-H covalent bonds would have different energies due to the different levels of orbital overlap.
However, with testing, it has been proven that in CH4, any hydrogen can be removed with the
same amount of energy. This means that every C-H covalent bond should have equal energies.
Once again, this means that the valence bond theory fails to explain the existence of CH 4. The
only way it can be explained is if when we had the exited state above, the 2s and the 3 2p orbitals
fused together to make four, equal energy sp3 hybrid orbitals. That would give us the following
configuration:

This explains how a carbon can have four equal energy bonds. The next section will explain the
various types of hybridization and how each type helps explain the structure of certain
molecules.

sp Hybridization
sp Hybridization can explain the linear structure in molecules. In it, the 2s orbital and one of the
2p orbitals hybridize to form two sp orbitals, each consisting of 50% s and 50% p character. The
front lobes face away from each other and form a straight line leaving a 180 angle between the
two orbitals. This formation minimizes electron repulsion. Because only one p orbital was used,
we are left with two unaltered 2p orbitals that the atom can use. These p orbitals are at right
angles to one another and to the line formed by the two sp orbitals.
Energy changes occurring in hybridization

Notice how the energy of the electrons lowers when hybridized.

These p orbitals come into play in compounds such as ethyne where they form two addition ?
bonds, resulting in in a triple bond. This only happens when two atoms, such as two carbons,
both have two p orbitals that each contain an electron. An sp hybrid orbital results when an s
orbital is combined with p orbital (Figure 2). We will get two sp hybrid orbitals since we started
with two orbitals (s and p). sphybridization results in a pair of directional sp hybrid orbitals
pointed in opposite directions. These hybridized orbitals result in higher electron density in the
bonding region for a sigma bond toward the left of the atom and for another sigma bond toward
the right. In addition, sp hybridization provides linear geometry with a bond angle of 180o.

Examples of sp Hybridization
Magnesium
Hydride
In magnesium hydride, the 3s orbital and one of the 3p orbitals from magnesium hybridize to
form two sp orbitals. The two frontal lobes of the sp orbitals face away from each other forming
a straight line leading to a linear structure. These two sp orbitals bond with the two 1s orbitals of
the two hydrogen atoms through sp-s orbital overlap.
Hybridization

Ethyne
The hybridization in ethyne is similar to the hybridization in magnesium hydride. For each

carbon, the 2s orbital hybridizes with one of the 2p orbitals to form two sp hybridized orbitals.
The frontal lobes of these orbitals face away from each other forming a straight line. The first
bond consists of sp-sp orbital overlap between the two carbons. Another two bonds consist of ssp orbital overlap between the sp hybridized orbitals of the carbons and the 1s orbitals of the
hydrogens. This leaves us with two p orbitals on each carbon that have a single carbon in them.
This allows for the formation of two ? bonds through p-p orbital overlap. The linear shape, or
180 angle, is formed because electron repulsion is minimized the greatest in this position.
Hybridization

sp2 hybridization
sp2 hybridization can explain the trigonal planar structure of molecules. In it, the 2s orbitals and
two of the 2p orbitals hybridize to form three sp orbitals, each consisting of 67% p and 33% s
character. The frontal lobes align themselves in the trigonal planar structure, pointing to the
corners of a triangle in order to minimize electron repulsion and to improve overlap. The
remaining p orbital remains unchanged and is perpendicular to the plane of the three sp2 orbitals.

Energy changes occurring in hybridization

Hybridization of an s orbital with two p orbitals (px and py) results in three sp2 hybrid orbitals that
are oriented at 120o angle to each other (Figure 3). Sp2 hybridization results in trigonal geometry.

Examples of sp2 hybridization


Aluminum
Trihydride
In aluminum trihydride, one 2s orbital and two 2p orbitals hybridize to form three sp 2 orbitals
that align themselves in the trigonal planar structure. The three Al sp 2 orbitals bond with with 1s
orbitals from the three hydrogens through sp2-s orbital overlap.

Hybridization

Ethene
Similar hybridization occurs in each carbon of ethene. For each carbon, one 2s orbital and two 2p
orbitals hybridize to form three sp 2orbitals. These hybridized orbitals align themselves in the
trigonal planar structure. For each carbon, two of these sp orbitals bond with two 1s hydrogen
orbitals through s-sp orbital overlap. The remaining sp2 orbitals on each carbon are bonded with
each other, forming a bond between each carbon through sp 2-sp2 orbital overlap. This leaves us
with the two p orbitals on each carbon that have a single carbon in them. These orbitals form a ?
bonds through p-p orbital overlap, creating a double bond between the two carbons. Because a
double bond was created, the overall structure of the ethene compound is linear. However, the
structure of each molecule in ethene, the two carbons, is still trigonal planar.
Hybridization

sp3 hybridization
sp3 hybridization can explain the tetrahedral structure of molecules. In it, the 2s orbitals and all
three of the 2p orbitals hybridize to form four sp orbitals, each consisting of 75% p character and
25% s character. The frontal lobes align themselves in the manner shown below. In this structure,
electron repulsion is minimized.
Energy changes occurring in hybridization

Hybridization of an s orbital with all three p orbitals (p x , py, and pz) results in four sp3 hybrid
orbitals. sp3 hybrid orbitals are oriented at bond angle of 109.5 o from each other. This
109.5o arrangement gives tetrahedral geometry (Figure 4).

Examples of sp3 hybridization


Methane
Because carbon plays such a significant role in organic chemistry, we will be using it as an
example here. Carbon's 2s and all three of its 3p orbitals hybridize to form four sp 3 orbitals.
These orbitals then bond with four hydrogen atoms through sp 3-s orbital overlap, creating
methane. The resulting shape is tetrahedral, since that minimizes electron repulsion.
Hybridization

Lone Pairs
Remember to take into account lone pairs of electrons. These lone pairs cannot double bond so
they are placed in their own hybrid orbital. This is why H2O is tetrahedral. We can also build sp3d
and sp3d2 hybrid orbitals if we go beyond s and p subshells.

References
1.

John Olmsted, Gregory M. Williams Chemistry: The Molecular Science Jones &
Bartlett Publishers 1996. 366-371
2.
Francis A. Carey Advanced Organic Chemistry Springer 2001. 4-6
3.
L. G. Wade, Jr. Whitman College Organic Chemistry Fifth Edition 2003

Practice Problems
Using the Lewis Structures, try to figure out the hybridization (sp, sp2, sp3) of the indicated atom
and indicate the atom's shape.
1. The carbon.

2. The oxygen.

3. The carbon on the right.

Answers
1. sp2- Trigonal Planar
The carbon has no lone pairs and is bonded to three hydrogens so we just need three hybrid
orbitals, aka sp2.
2. sp3 - Tetrahedral
Don't forget to take into account all the lone pairs. Every lone pair needs it own hybrid
orbital. That makes three hybrid orbitals for lone pairs and the oxygen is bonded to one
hydrogen which requires another sp3 orbital. That makes 4 orbitals, aka sp3.
3. sp - Linear
The carbon is bonded to two other atoms, that means it needs two hybrid orbitals, aka sp.
An easy way to figure out what hybridization an atom has is to just count the number of atoms
bonded to it and the number of lone pairs. Double and triple bonds still count as being only
bonded to one atom. Use this method to go over the above problems again and make sure you
understand it. It's a lot easier to figure out the hybridization this way.

Contributors

Harpreet Chima (UCD), Farah Yasmeen


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Sigma and Pi Bonds


A description of the double bond is the sigma-pi model shown in Fig. 1. In this case only two of
the p orbitals on each C atom are involved in the formation of hybrids. Consequently sp2 hybrids
are formed, separated by an angle of 120. Two of these hybrids from each C atom overlap with
H 1s orbitals, while the third overlaps with an sp2hybrid on the other C atom. This overlap
directly between the two C atoms is called asigma bond, and is abbreviated by the Greek letter
. This orbital has no nodes:electron density exists continuously from around one atom to the
other atom.

Figure 1 The sigma-pi model of a double bond. Three sp2 hybrids around each carbon atom are indicated in color. Two of these overlap directly
between the carbon atoms to form the bond. Two p orbitals, one on each C atom, are shown in gray. These overlap sideways to form a bond,
also shown in gray.

No MO selected
N1 Ag -277.1281
N2 B1u -277.1039
N3 Ag -20.5375

No MO

HOMO

LUMO
MO cutoff:
0.01
To view the sigma bonding orbital, select N6. This is actually
sigma bonding between C-C and some sigma-like bonding
around the Hs as well. Focus on the yellow portion. By
selecting N8 HOMO, you can see the pi orbital represented by
the two lobes.

The sp2 hybrid orbitals on each carbon atom involve the 2s and two of the 2p orbitals, leaving a
single 2p orbital on each carbon atom. A second carbon-carbon bond is formed by the overlap of
these two remaining p orbitals. This is called a pi bond, Greek letter . The pi bond ( bond) has
two halvesone above the plane of the molecule, and the other below it. Each of the two
electrons in the pi bond ( bond) exists both above and below the plane of the four H atoms and
the two C atoms. The pi bond can be thought of as a standing wave with a single node in the
plane of the molecule.
If your workstation is enabled for JCE Software, you will see two videos below which compare
the behavior of a standing wave with zero nodes versus a standing wave with one node
(otherwise, see the drum animation below). The wave with a single node has higher energy. The
sigma bond between the two carbon atoms does not have a node in the plane of the molecule.
The pi bond between the two carbon atoms has one node in the plane of the molecule. Thus the
pi molecular orbital is higher in energy and is the highest occupied molecular orbital (the
HOMO).
(a) No Nodes
(b) Single Node
Standing Waves on a Wave Demonstrator. (a) The lowest
energy form of a standing wave has no nodes. This is like the
continual electron density in all directions around the sigma
bonding orbital. (b) The second lowest energy standing wave
has a single node. This node is akin to the shape of the pi bond
where there is no electron density along the plane.

Alternatively, we can envision the molecular orbitals with the Drum Model described earlier.
Imagine the two atoms opposite one another where a diagonal meets the edge of the drum at
extreme left and right points. The m1,0 mode has no nodes, so the maximum amplitude of the
standing wave is between the atoms, representing a high electron density sigma bond. The
m2,1 mode has a linear node between the atoms, and maximum amplitude in front of, and behind,
the node, representing the pi bond. In 3D, this linear node would be a plane, separating the two
lobes of high electron density that constitute the pi bond. Because the pi bond has less electron
density between the atoms, it is of higher energy in the MO diagram and is weaker than the
sigma bond.

mode m1,0

mode m2,1

Overall this sigma-pi picture of the double bond is reminiscent of a hot dog in a bun. The sigma
bond ( bond) corresponds to the frankfurter, while the pi bond corresponds to the bun on either
side of it.
Although the sigma-pi picture is more complex than the bent-bond picture of the double bond, it
is much used by organic chemists (those chemists interested in carboncompounds). The sigma-pi
model is especially helpful in understanding what happens when visible light or other radiation is
absorbed by a molecule. Further discussion on this topic is found in the sections on Spectra and
Structure of Atoms and Molecules.

Figure 2 Dot-density diagrams comparing the sigma-pi and bent-bond models of the double bond. (a) The sigma-pi model. The bond is in color
and the bond is in gray. (b) The bent-bond model. One lies above the two nuclei and the other below. Since both diagrams are dot-for-dot the
same, they are both describing the same physical reality.

In actual fact the difference between the two models of the double bond (the first model
described here and the second found in the section on Orbital Descriptions of Multiple Bonds) is
more apparent than real. They are related to each other in much the same way as s and p orbitals
are related to sp hybrids. Figure 2 shows two dot-density diagrams for a carbon-carbon double
bond in a plane through both carbon nuclei but at right angles to the plane of the molecule.
Figure 2a corresponds to a sigma-pi model with the sigma bond ( bond) in color and the pi
bond in gray. Figure 2b shows two bent bonds. Careful inspection reveals that both diagrams are
dot-for-dot the same. Only the color coding of the dots is different. Thus the bent-bond and
sigma-pi models of the double bond are just two different ways of dividing up the same overall
electron density.
A similar situation applies to triple bonds, such as that found in a molecule of ethyne
(acetylene),
. As shown in Fig. 3a,we can regard this triple bond as being the
result of three overlaps of sp3 hybrids on different carbon atoms forming three bent bonds.
Alternatively we can regard it as being composed of one sigma bond and two pi bonds, the sigma

bond being due to the overlap of an sp hybrid from each carbon atom. Again both pictures of the
bond correspond to the same overall electron density, and hence both are describing the same
physical reality. We can use whichever one seems more convenient for the problem under
consideration.

Figure 3 Two alternative models for the triple bond in ethyne,

. (a) Three sp3 hybrids from each carbon atom overlap to

form three bent bonds. (b) Two sp hybrids overlap to form the sigma bond. Two p orbitals on one carbon overlap with two on the other to form
two pi bonds (one in light gray, the other in dark gray). Though these two models appear to be different, the indistinguishability of electrons
makes them exactly equivalent.

N8 pi.g 1.4267
N9 pi.g 1.4267
N10 sigma.u 2.8730
N11 sigma.g 4.0499

No MO

HOMO

LUMO

MO cutoff:
0.01
The orbitals can be viewed by selecting from the orbital menu at right. Again, these orbitals are more easily represented using an
MO Cutoff of 0.005. By selecting By selecting N1 you can see the sigma bonding orbital. The two pi bonding orbitals can be viewed
by selecting N6 and N7. If you rotate the molecule so that we view the molecule along the H-C-C-H line, you can switch back and
forth between N6 and N7 to see the orientation in space.

Sigma and Pi Bonds


Simply put, a sigma bond is a single covalent bond.
The electron pair is located between the two atoms involved in the bonding.
A pi bond uses the p-orbitals that are located above and below these atoms.

The overlap is a pi-bond. The image above is actually only 1 pi-bond.


A p-orbital is has a shape of a dumbbell. So there are 2 regions of overlapping.

So, the grey bond is a sigma bond (a single bond), the clouds are a pi (this is the
second bond or your double bond).
So, how can we have triple bonds? Use the image below
The region of space above and below the sigma bond (single bond) are already
occupied. The p-orbitals (Pink) can wrap around to the left and right of the sigma
bond. This overlap is 90o from the other pi-bond (blue) that is already in place. So it is
possible to have 2-pi bonds and a sigma or what we call a triple bond.

In conclusion, a triple bond is a sigma bond located directly between the atoms, and 2
pi bonds located above and below, and around the sides of the 2 atoms.
Every bond has a sigma. Doubles have a sigma and a pi. Triples have a sigma and two
pi bonds.