Orbital hybridisation

From Wikipedia, the free encyclopedia

Not to be confused with s-p mixing in Molecular Orbital theory. See Molecular orbital diagram.
In chemistry, hybridisation (or hybridization) is the concept of mixing atomic orbitals into new hybrid orbitals (with
different energies, shapes, etc., than the component atomic orbitals) 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 sp
x
and sd
x
terminology
3 Types of hybridisation
3.1 sp
3
hybrids
3.2 sp
2
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 Resonance description
5.2.1 Main group compounds with lone pairs
6 Clarifying misconceptions
6.1 VSEPR electron domains and hybrid orbitals are different
6.2 Exclusion of d orbitals in main group compounds
6.3 Exclusion of p orbitals in transition metal complexes
7 Hybridization theory vs. Molecular Orbital theory
8 See also
9 References
10 External links
Historical development [edit]
Chemist Linus Pauling first developed the hybridisation theory in 1931 in order to explain the structure of simple
molecules such as methane (CH
4
) using atomic orbitals.
[2]
Pauling pointed out that a carbon atom forms four bonds
by using one s and three p orbitals, so that "it might be inferred" that a carbon atom would form three bonds at right
angles (using p orbitals) and a fourth weaker bond using the s orbital in some arbitrary direction. In reality however,
methane has four bonds of equivalent strength separated by the tetrahedral bond angle of 109.5. Pauling explained
this by supposing that in the presence of four hydrogen atoms, the s and p orbitals form four equivalent combinations
or hybrid orbitals, each denoted by sp
3
to indicate its composition, which are directed along the four C-H bonds.
[3]
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 rationalising the structures of organic 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 neutral atom
for which the Schrdinger equation can be solved exactly. In heavier atoms, such as 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.
sp
x
and sd
x
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 each carbonhydrogen bond consists of 25% s character and 75% p character and is
thus described as sp
3
(read as s-p-three) hybridised. Quantum mechanics describes this hybrid as an sp
3
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 a sigma 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 N
2

2
= 3/4.
For atoms forming equivalent hybrids with no lone pairs, there is a correspondence to the number and type of orbitals
used. Thus sp
3
hybrids in methane are formed from one s and three p orbitals. However, in other cases, there may
be no such correspondence. For example, the two bond-forming hybrid orbitals of oxygen in water can be described
as sp
4
, which means that they have 20% s character and 80% p character, but does not imply that they are formed
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Four sp
3
orbitals.
Three sp
2
orbitals.
Ethene structure
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 sp
2.5
are also readily described. For more information see variable hybridization.
An analogous notation is used to describe sd
x
hybrids. For example, the permanganate ion (MnO
4

) has sd
3
hybridisation with orbitals that are 25% s and 75% d.
Types of hybridisation [edit]
sp
3
hybrids [edit]
Hybridisation describes the bonding atoms from an atom's point of view. That is, for a
tetrahedrally coordinated carbon (e.g., methane CH
4
), the carbon should have 4 orbitals
with the correct symmetry to bond to the 4 hydrogen atoms.
Carbon's ground state configuration is 1s
2
2s
2
2p
x
1
2p
y
1
or more easily read:
C

1s 2s 2p
x
2p
y
2p
z
The carbon atom can utilize its two singly occupied p-type orbitals (the designations p
x
p
y
or p
z
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 CH
2
, 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.
C*

1s 2s 2p
x
2p
y
2p
z
As the energy released by formation of two additional bonds more than compensates for the excitation energy
required, 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. A set of four equivalent orbitals can be obtained which are linear
combinations of the valence-shell (core orbitals are almost never involved in bonding) s and p wave functions
[4]
which
are the four sp
3
hybrids.
C*

1s sp
3
sp
3
sp
3
sp
3
In CH
4
, four sp
3
hybrid orbitals are overlapped by hydrogen 1s orbitals, yielding four (sigma) bonds (that is, four
single covalent bonds) of equal length and strength.
translates into
sp
2
hybrids [edit]
Other carbon based compounds and other molecules may be explained in a similar way
as methane. For example, ethene (C
2
H
4
) has a double bond between the carbons.
For this molecule, carbon will sp
2
hybridise, because one (pi) bond is required for the
double bond between the carbons, and only three bonds are formed per carbon atom.
In sp
2
hybridisation the 2s orbital is mixed with only two of the three available 2p
orbitals:
C*

1s sp
2
sp
2
sp
2
2p
forming a total of three sp
2
orbitals with one p orbital remaining. In ethylene (ethene) the two
carbon atoms form a bond by overlapping two sp
2
orbitals and each carbon atom forms two
covalent bonds with hydrogen by ssp
2
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]
The chemical bonding in compounds such as alkynes with triple bonds is explained by sp
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Two sp orbitals
The chemical bonding in compounds such as alkynes with triple bonds is explained by sp
hybridisation.
C*

1s sp sp 2p 2p
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) (C
2
H
2
) 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 since the angles between bonds are (approximately) equal to the
angles between hybrid orbitals, as explained above for the tetrahedral geometry of methane. As another example, the
three sp
2
hybrid orbitals are at angles of 120 to each other, so this hybridisation favours trigonal planar molecular
geometry with bond angles of 120. Other examples are given in the table below.
Classification Main group Transition metal
[5]
AX
2
Linear (180)
sp hybridisation
E.g., CO
2
Bent (90)
sd hybridisation
E.g., VO
2
+
AX
3
Trigonal planar (120)
sp
2
hybridisation
E.g., BCl
3
Trigonal pyramidal (90)
sd
2
hybridisation
E.g., CrO
3
AX
4
Tetrahedral (109.5)
sp
3
hybridisation
E.g., CCl
4
Tetrahedral (109.5)
sd
3
hybridisation
E.g., MnO
4

AX
5
-
Square pyramidal (66, 114)
[6][7]
sd
4
hybridisation
E.g., Ta(CH
3
)
5
AX
6
-
Trigonal prismatic (63, 117)
[6][7]
sd
5
hybridisation
E.g., W(CH
3
)
6
Main group compounds with lone pairs [edit]
For main group compounds with lone electron pairs, the s orbital lone pair can be hybridised to a certain extent with
the bond pairs.
[8]
This is analogous to s-p mixing in molecular orbital theory, and maximizes energetic stability
according to the Walsh diagram for the molecule.
Trigonal pyramidal (AX
3
E
1
)
The s-orbital can be hybridised with the three p-orbital bonds to give bond angles greater than 90.
Ex. NH
3
Bent (AX
2
E
1-2
)
The 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, the in-plane and out-of-plane
lone pairs are inequivalent, contrary to the common picture depicted by VSEPR theory (see below).
Exs. SO
2
, H
2
O
Monocoordinate (AX
1
E
1-3
)
The 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 not equivalent to the s-rich lone pair.
Exs. 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 AX
5
and
above, as well as for transition metal complexes, using the hybridisation scheme first proposed by Pauling.
Classification Main group Transition metal
AX
2
-
Linear (180)
sp hybridisation
E.g., Ag(NH
3
)
2
+
AX
3
-
Trigonal planar (120)
sp
2
hybridisation
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E.g., Cu(CN)
3
2
AX
4
-
Square planar (90)
dsp
2
hybridisation
E.g., PtCl
4
2
AX
5
Trigonal bipyramidal (90, 120)
sp
3
d hybridisation
E.g., PCl
5
Trigonal bipyramidal (90, 120)
dsp
3
hybridisation
E.g., Fe(CO)
5
AX
6
Octahedral (90)
sp
3
d
2
hybridisation
E.g., SF
6
Octahedral (90)
d
2
sp
3
hybridisation
E.g., Mo(CO)
6
AX
7
Pentagonal bipyramidal (90, 72)
sp
3
d
3
hybridisation
E.g., IF
7
Pentagonal bipyramidal (90, 72)
d
3
sp
3
hybridisation
E.g., V(CN)
7
4
AX
8
Square antiprismatic
sp
3
d
4
hybridisation
E.g., IF
8

Square antiprismatic
d
4
sp
3
hybridisation
E.g., Re(CN)
8
3
AX
9
-
Tricapped trigonal prismatic
d
5
sp
3
hybridisation
E.g., ReH
9
2
In this notation, d orbitals of main group atoms are listed after the s and p orbitals since they have the same principal
quantum number (n), while d orbitals of transition metals are listed first since the s and p orbitals have a higher n.
Thus for AX
5
molecules, sp
3
d hybridisation in the P atom involves 3s, 3p and 3d orbitals, while dsp
3
for Fe involves
3d, 4s and 4p orbitals.
However, hybridisation of s, p and d orbitals together is no longer accepted, 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).
Resonance description [edit]
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 a maximum of 8
[9]
(or 12 for transition metals). This requires an explanation that invokes sigma
resonance in addition to hybridisation, which implies that each resonance structure has its own hybridisation scheme.
As a guideline, all resonance structures have to obey the octet rule for main group compounds and the dodectet (12)
rule for transition metal complexes.
Classification Main group Transition metal
AX
2
-
Linear (180)
AX
3
-
Trigonal planar (120)
AX
4
-
Square planar (90)
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AX
5
Trigonal bipyramidal (90, 120) Trigonal bipyramidal (90, 120)
Fractional hybridisation (s and d orbitals)
E.g., Fe(CO)
5
AX
6
Octahedral (90) Octahedral (90)
AX
7
Pentagonal bipyramidal (90, 72) Pentagonal bipyramidal (90, 72)
Fractional hybridisation (s and three d orbitals)
E.g., V(CN)
7
4
AX
8
Square antiprismatic Square antiprismatic
Fractional hybridisation (s and three p orbitals)
E.g., IF
8

Fractional hybridisation (s and four d orbitals)

E.g., Re(CN)
8
3
AX
9
-
Tricapped trigonal prismatic
Fractional hybridisation (s and five d orbitals)
E.g., ReH
9
2
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 "resonant bonding" component and the "regular bonding" component. The "regular bonding"
component has the same description (see above), while the "resonant bonding" component consists of resonating
bonds utilizing p orbitals. The table below shows how each shape is related to the two components and their
respective descriptions.
Regular bonding component (marked in red)
Bent Monocoordinate -
Resonant
bonding
component
Linear axis
Seesaw (AX
4
E
1
) (90,
180, >90)
T-shaped (AX
3
E
2
) (90, 180) Linear (AX
2
E
3
) (180)
Square
planar
equator
-
Square pyramidal (AX
5
E
1
) (90, 90) Square planar (AX
4
E
2
) (90)
Pentagonal pyramidal (AX
6
E
1
) (90,
72)
Pentagonal planar (AX
5
E
2
) (72)
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Pentagonal
planar
equator
-
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
[8]
despite its widespread usage in many textbooks. For example, following the guidelines of
VSEPR, the hybridization of the oxygen in water is described with two equivalent lone electron-pairs.
[10]
However,
molecular orbital calculations give orbitals that reflect the C
2v
symmetry of the molecule.
[11]
One of the two lone pairs
is in a pure p-type orbital, with its electron density perpendicular to the HOH framework.
[12]
The other lone pair is in
an approximately sp
0.8
orbital that is in the same plane as the HOH bonding.
[12]
Photoelectron spectra confirm the
presence of two different energies for the nonbonded electrons.
[13]
Exclusion 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.
[14]
Exclusion 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, recent molecular orbital calculations have found that such p orbital participation
in bonding is insignificant,
[15][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.
Hybridization theory vs. Molecular Orbital 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 UV-visible spectra which
correspond to electronic transitions between delocalized orbitals. From a pedagogical perspective, the hybridisation
approach tends to over-emphasize localisation of bonding electrons and does not effectively embrace molecular
symmetry as does MO theory.
See also [edit]
Linear combination of atomic orbitals molecular orbital method
MO diagrams
Ligand field theory
Crystal field theory
References [edit]
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1. ^ Gillespie, R.J. (2004), "Teaching molecular geometry with the VSEPR model", Journal of Chemical Education 81 (3):
298304, Bibcode:2004JChEd..81..298G , doi:10.1021/ed081p298
2. ^ Pauling, L. (1931), "The nature of the chemical bond. Application of results obtained from the quantum mechanics and
from a theory of paramagnetic susceptibility to the structure of molecules", Journal of the American Chemical Society 53
(4): 13671400, doi:10.1021/ja01355a027
3. ^ L. Pauling The Nature of the Chemical Bond (3rd ed., Oxford University Press 1960) p.111-120.
4. ^ McMurray, J. (1995). Chemistry Annotated Instructors Edition (4th ed.). Prentice Hall. p. 272. ISBN 978-0-131-40221-8
5. ^ Weinhold, Frank; Landis, Clark R. (2005). Valency and bonding: A Natural Bond Orbital Donor-Acceptor Perspective.
Cambridge: Cambridge University Press. pp. 381383. ISBN 978-0-521-83128-4.
6. ^
a

b
Kaupp, Martin (2001). " "Non-VSEPR" Structures and Bonding in d(0) Systems". AngewChem Int Ed Engl. 40 (1):
35343565. doi:10.1002/1521-3773(20011001)40:19<3534::AID-ANIE3534>3.0.CO;2-# .
7. ^
a

b
King, R. Bruce (2000). "Atomic orbitals, symmetry, and coordination polyhedra". Coordination Chemistry Reviews
197: 141168.
8. ^
a

b
Weinhold, Frank. "Rabbit Ears Hybrids, VSEPR Sterics, and Other Orbital Absurdities" . University of Wisconsin.
Retrieved 2012-11-11.
9. ^ David L. Cooper , Terry P. Cunningham , Joseph Gerratt , Peter B. Karadakov, Mario Raimondi (1994). "Chemical
Bonding to Hypercoordinate Second-Row Atoms: d Orbital Participation versus Democracy". Journal of the American
Chemical Society 116 (10): 44144426. doi:10.1021/ja00089a033 .
10. ^ Petrucci R.H., Harwood W.S. and Herring F.G. "General Chemistry. Principles and Modern Applications" (Prentice-Hall
8th edn 2002) p. 441
11. ^ Levine I.N. Quantum chemistry (4th edn, Prentice-Hall) p. 4702
12. ^
a

b
Laing, Michael J. Chem. Educ. (1987) 64, 124128 "No rabbit ears on water. The structure of the water molecule:
What should we tell the students?"
13. ^ Levine p. 475
14. ^ E. Magnusson. Hypercoordinate molecules of second-row elements: d functions or d orbitals? J. Am. Chem. Soc.
1990, 112, 7940-7951. doi:10.1021/ja00178a014
15. ^ C. R. Landis, F. Weinhold (2007). "Valence and extra-valence orbitals in main group and transition metal bonding".
Journal of Computational Chemistry 28 (1): 198203. doi:10.1002/jcc.20492 .
16. ^ ODonnell, Mark (2012). "Investigating P-Orbital Character In Transition Metal-to-Ligand Bonding" . Brunswick, ME:
Bowdoin College. Retrieved 2012-09-16.
17. ^ Clayden, Jonathan; Greeves, Nick; Warren, Stuart; Wothers, Peter (2001). Organic Chemistry (1st ed.). Oxford
University Press. p. 105. ISBN 978-0-19-850346-0.
18. ^ Organic Chemistry, Third Edition Marye Anne Fox James K. Whitesell 2003 ISBN 978-0-7637-3586-9
19. ^ Organic Chemistry 3rd Ed. 2001 Paula Yurkanis Bruice ISBN 978-0-130-17858-9
External links [edit]
Covalent Bonds and Molecular Structure
Hybridisation flash movie
Hybrid orbital 3D preview program in OpenGL
Understanding Concepts: Molecular Orbitals
Categories: Chemical bonding Quantum chemistry Stereochemistry
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