- plane_frame.pdf
- conceptual foundations - the number system part 3
- Calculus for 2011
- classicallaminationtheory-matlab program.pdf
- G4 Profiles
- Rotation
- Category Plots
- Mech Intro2 14.0 L04 Joints
- CHOICES 3 - C&C Manual
- EMC620S-Quiz2-2013.doc
- Unigraphics NX Sketching Fundamentals MT10028 (Student Guide)
- Chem 120 Fall 2012 PS1 Answer Key(1)
- Modul Edit Coordinates
- Trial 2003 Admt P1
- Laue & Bravis Crystal Lattice
- Molecular dynamics simulation of dipole interactions
- MIT8_01SC_slides03
- Translation & Reflection
- Robotics Review
- Lecture 7
- module two ubd 2014 - complete
- Sinumerik 810T 820T GA3 Programming
- 13plus_mathssamplepaper2009_63369_1
- Burghardt 2005 Ica Pca
- 329003432-Synthetic-FFR-2.docx
- Grouped Frequency Histogram
- eNGINEER
- goc 2.pdf
- Jntu Anan 3 2 Me Cadcam Set 1
- Manual SmartBars
- Instrumental Analysis Spectroscopy.ppt12
- IR Spectroscopu Ambo
- COUNCIL OF MINISTERS REGULATIONS TO PROVIDE FOR THE IMPLEMEN.pdf
- Scientific Communication
- Aspirin 2
- Spectroscopy Lecture note
- Saponification
- Spectroscopy
- UV Vis Exercises
- Scientific Communication III
- NMR MS Spectroscopy Ambo2 b
- AChem Notes
- Instrumental Analysis Spectroscopy.ppt12
- Introduction to Statistics for Chemistry - Copy
- 411 Unit 3F
- Research Methodology,12
- Exercises For spectroscopic techniques-Ambo 2012.docx
- Research Methodology,12
- Module 4
- Research Methodology,12
- Research Methodology,
- Schrodinger Eq n
- Research Methodology,12
- kaizene
- Agreement Form
- Book
- 04 KZN BG Form Process 5S Evaluation Sheet(Sample)
- Agreement Form
- 04 KZN BG Form Process 5S Evaluation Sheet(Sample)

Inorganic Chemistry III (Chem. 4081) Lecture Note

AMBO UNIVERSITY

COLLEGE OF NATURAL AND COMPUTITIONAL SCIENCE

DEPARTMENT OF CHEMISTRY

INORGANIC CHEMISTRY III

(CHEM 4081)

Unit 1

Symmetry and Group Theory

1.1

Introduction

What Is Symmetry?

The term symmetry is derived from the Greek word “symmetria” which means “measured

together”. An object is symmetric if one part (e.g. one side) of it is the same* as all of the other

parts. Symmetry is the notion that an object of study may look the same from different points

of view. For instance; A sphere is more symmetrical than a cube because it looks the same after

rotation through any angle about the diameter. A cube looks the same only if it is rotated

through certain angels about specifc axis, such as 90o, 180o, or 270o about an axis passing

through the centers of any of its opposite faces, or by 120oor 240o about an axis passing through

any of the opposite corners.

When we say that a molecule has symmetry we mean that certain parts of it can be interchanged

with others without althering either identity or the orientaion of the molecule. The interchangeable parts are said to be equivalents to one another by symmetry, for example, a

Trigonal bipyramidal molecule such as PF5.

In this molecule we can see that, the three

equatorial P-F bonds to F1, F2 and F3 are

equivalent. They have the same bond

strength, bond angle, and the same type of

spacilal relation to the remainder of

1

Compailled by Kebede Humnessa Gemeda (MSc, Inoganic Chemistry),2014

**the molecule. Any permutation of these three bonds are among them selves leads to a molecule
**

indisistinguishible from the original. Similarly, the axial P-F bond F4 and F5 are equivalent. But

axial and equatorial bnds are different types (eg. They have different length and bond angle), and

if one of each were to be interchanged , the molecule would be noticiably , on an intuitive bases

You know intuitively if something is symmetric but we require a precise method to describe how

an object or molecule is symmetric.the first set of tools is a set of symetry operation.

Here are also examples of different molecules which remain the same after certain symmetry

operations: NH3, H2O, C6H6, CBrClF. In general, an action which leaves the object looking the

same after a transformation is called a symmetry operation. Typical symmetry operations

include rotations, reflections, and inversions. There is a corresponding symmetry element for

each symmetry operation, which is the point, line, or plane with respect to which the symmetry

operation is performed. For instance, a rotation is carried out around an axis; a reflection is

carried out in a plane, while an inversion is carried out in a point.

1.2Symmetry elements and operations

A symmetry operation is an action that leaves an object looking the same after it has been

carried out. For example, if we take a molecule of water, H2O (HOH), and rotate it by 180°

about an axis passing through the central O atom it will look the same as before. It will also look

the same if we reflect it through either of two mirror planes, as shown in the figure below.

**The square planar PtCl42- ion is said to be a highly symmetric ion because it contains a large
**

number of symmetry elements. Each symmetry operation has a corresponding symmetry

element, which is the axis, plane, line or point with respect to which the symmetry operation is

carried out. The symmetry element consists of all the points that stay in the same place when

the symmetry operation is performed. In a rotation, the lines of points that stay in the same place

constitute a symmetry axis; in a reflection the points that remain unchanged make up a plane of

symmetry.

The symmetry elements that a molecule may possess are:

1. The identity- E. The identity operation is equivalent to doing nothing or rtation about

360o (C1 operation) and has no symmetry element but it is a required member of each

symmetry group, and the corresponding symmetry element is the entire molecule. Every

molecule has at least this element. Thus, operation with E will change neither the positions of

the atoms nor the phases of the pz-orbitals. Consider the following description;

**The trasformational matrix for identity element is a unit matrix, or unit matrix given above in
**

squere bracket. The example; of the molecule which has only the identity symmetry

operation is C3H6O3, DNA and CHClBrF.

2. An n-fold axis of rotation - C n. Rotation by 360°/n leaves the molecule unchanged.

Particularly, the operation C1 is a rotation through 3600 which is equivalent to the identity E.

H2O molecule has one twofold axis, C 2. NH3 molecule has one threefold axis,C3, which is

associated with two symmetry operations: 1200, rotation C3 and 240o (or -1200) rotation

C23.C6H6 molecule has one six-fold axis C6, and six twofold axes C2. All linear molecules

including all diatomics has C∞ axis because rotation on any angle remains the molecule the

same. Some molecules have more than one C axis, in which case the one with the highest

value of n is called the principal axis, and is designated as the z-axis. Note that by

convention rotations are counterclockwise about the z-axis. Thus the z-axis in PtCl42- is

perpendicular to the plane of the ion. This axis is actually three symmetry elements since

rotations by π/2, π, and 3π /2 about this axis all result in no change in the molecule. These

three axes are referred to as C4, C42 = C2 and C43, respectively.

The proper rotation (clockwise direction) about the z axis can be described by the following

matrix equation.

**3. A plane of symmetry (refelection) -σ. Reflection in the plane leaves the molecule looking
**

the same. Reflection can be made through three different types of planes: vertical plane

(σv) contain the principle axis, horizontal planes (σh) are perpendicular to the principle axis

and dihedral planes (σd) contain the principle axis and bisect two C 2 axes. The distinction

between vertical and dihedral is often unclear. Where appropriate, planes bisecting bond

angles will be designated as dihedral while those containing bonds will be designated as

vertical. See figure

Figure I-3. The

reflection through

planes on the atoms

effect of

the symmetry

and the

chlorine pz orbitals

in PtCl42-

**In PtCl42-, the
**

planes

containing the zaxis (σv and

σd) will not

change the

phase of the pz

orbitals

while reflection

through the

plane

perpendicular to the z-axis (σh) does invert them (figure I-3). Thus, PtCl42-contains: σv(XZ ) and

σv(YZ ), σh(XY) and σd(a) and σd (b) or five planes of symmetry. Note that a and b planes are

**defined as those planes perpendicular to the plane of the ion and containing a and b rotational
**

axes.

If the mirror plane coincides with the xy, xz, or yz Cartesian planes, they can be described by the

following matrix equations:

σxσ=E

4. A centre of symmetry (inversion) -i. Inversion through the centre of symmetry leaves the

molecule unchanged. A Center of Inversion (i) takes all (x,y,z) → (-x,-y,-z). This operation

can be performed by a C(z) which takes (x,y,z) → (-x,-y,+z) followed by a σ(xy) which

inverts z, i.e., i= C2σh = S2. Since i and S2 are equivalent, S2 is not usually used.

Inversion consists of passing each point through the centre of inversion and out to the same

distance on the other side of the molecule. An example of a molecule with a centre of inversion

is shown below.

Figure I-4. The effect of improper rotations on the atoms and the chlorine in PtCl42-

The inversion operation changes the sign of all the x, y and z coordinates:

**5. An n-fold improper rotation (also called a rotary-reflection) -Sn. The rotary reflection
**

operation consists of rotating through an angle 360°/n about the axis, followed by reflecting

in a plane perpendicular to the axis.that is, (Sn) is a Cn followed by a σh. Note that Sn1 is the

same as reflection and S is the same as inversion. The molecule shown above has two S 2

axes. SincePtCl42- is a planar ion; the Z-axis is an element for both proper and improper

rotations. See figure I-4. Note that an S4 results in the same numbering as a C4, but the

phases of the p orbitals are changed.

The identity E and rotations Cn are symmetry operations that could actually be carried out on

a molecule. For this reason they are called proper symmetry operations. Reflections,

inversions and improper rotations can only be imagined (it is not actually possible to turn a

molecule into its mirror image or to invert it without some fairly drastic rearrangement of

chemical bonds) and as such, are termed improper symmetry operations, Sn.

The improper rotation about the z axis can be described as a proper rotation followed by

changing the sign of the z coordinate.

**When n is even, Sn generates n operations.
**

When n is odd, Sn generates 2n operations.

Snn is equivalent to σ, and Sn2n is equivalent to E.

S1 = σh;

S2 = i

A note on axis definitions: Conventionally, when imposing a set of Cartesian axes on a

molecule (as we will need to do later on in the course), the z axis lies along the principal axis of

the molecule, the x axis lies in the plane of the molecule (or in a plane containing the largest

number of atoms if the molecule is non-planar), and they axis makes up a right handed axis

system.

1.3. Point Groups and Molecular Symmetry

It is only possible for certain combinations of symmetry elements to be present in a molecule (or

any other object). As a result, we may group together molecules that possess the same

symmetry elements and classify molecules according to their symmetry. These groups of

symmetry elements are called point groups (due to the fact that there is at least one point in

space that remains unchanged no matter which symmetry operation from the group is applied).

There are two systems of notation for labeling symmetry groups, called the Schoenflies and

Hermann-Mauguin (or International) systems. The symmetry of individual molecules is usually

described using the Schoenflies notation, and we shall be using this notation for the remainder of

the course1.

Note: Some of the point groups share their names with symmetry operations, so be careful you

don’t mix up the two. It is usually clear from the context which one is being referred to.

The molecular point groups are listed below:

**1. C1 – contains only the identity (a C1 rotation is a rotation by 360° and is the same as the
**

identity operation E) e.g. CHDFCl.

2. Ci- contains the identity E and a centre of inversion i.

3. Cσ - contains the identity E and a plane of reflection σ.

4. Cn – contains the identity and an n-fold axis of rotation.

5. Cnv – contains the identity, an n-fold axis of rotation, and n vertical mirror planes σv.

**6. Cnh- contains the identity, an n-fold axis of rotation, and a horizontal reflection plane σh
**

(note that in C2h this combination of symmetry elements automatically implies a centre of

inversion).

**7. Dn - contains the identity, an n-fold axis of rotation, and n 2-fold rotations about axes
**

perpendicular to the principal axis

8. Dnh contains the same symmetry elements as Dn with the addition of a horizontal mirror

plane.

**9. Dnd- contains the same symmetry elements as Dn with the addition of n dihedral mirror
**

planes.

10. Sn - contains the identity and one Sn axis. Note that molecules only belong to S2 if they have

not already been classified in terms of one of the preceding point groups (e.g. S n is the same

as Ci, and a molecule with this symmetry would already have been classified).

High order point groups:-There are several special point groups. Molecules having three or

more high symmetry elements may belong to one of the following: Molecules with multiple

higher-order rotation axes, the cubic groups T, Th, Td, O, Oh and Ih.

The following groups are the cubic groups, which contain more than one principal axis. They

separate into thetetrahedral groups (Td and Th) and the octahedral groups (O and Oh). The

icosahedral group also exists but is not included below.

11. Tetrahedral; Td:- species with tetrahedral symmetry. Eg. CH4. Contains all the symmetry

elements of a regular tetrahedron, including the identity, 4 C. C2 axes, 6 dihedral mirror

planes, and 3 S4 axis; e.g. CH4.

**12. Tetrahedral; T - as for Td but no planes of reflection. Contains all the symmetry elements of
**

Td without σh.

Eg. C(CH3)4

13. Tetrahedral;Th– Contains all the symmetry elements of Td with σh. as for T but contains a

centre of inversion

14. Oh – the group of the regular octahedron e.g. SF6.

15. Octahedral: O - For O group, symmetry elements are E, 3C4, 4C3, and 6C2 as for Oh but with

no planes of reflection. And symmetry operations are {E, 8C3, 3C2፣ 6C4, 6C2} . The order

of O group is 24.

16. Icosahedral, Ih:-contains 6C5 asis and a total of 120 symmetry elements.

Dodecahedron

Icosahedrons

17.Highly symmetrical molecules:A few geometries have several, equivalent, highest order axes. Two geometries most

important:

Linear molecules: C∞v, and D∞h

Do infact fit in to scheme but they have an infinite number of symmetry operations.

Molecular axis ia C∞v-rotation by any arbitirary angle (360/∞)o, so infinite number of rotations.

Also any plane containing axis is symmetry plane, so infinite number of planes of symmetry.

Divide linear molecules into two groups:

i. Molecules with no centre of symmetry; This point groups conyains a C∞axis and an infinite

number of σv planes eg, NCN, OCS and hetrodiatomic molecules.

ii.

Molecules with centre of symmetry: eg. CO2, and homodiatomic molecules.D∞h.

**The final group is the full rotation group R 3, which consists of an infinite number of C n axes with
**

all possible values of n and describes the symmetry of a sphere. Atoms (but no molecules)

belong to R3, and the group has important applications in atomic quantum mechanics. However,

we won’t be treating it any further here.

Table 1.1 Common Point Groups and Their Symmetry Elements

Point Group

Symmetry Elements Present

C1

E

Cs

E, σh

Ci

E, i

Cn

E, Cn

Dn

n = odd

E, Cn, nC2

Dn

n = even

E, Cn, n/2C2´, n/2C2´´

Cnv

n = odd

E, Cn, nσv

Cnv

n = even

E, Cn, n/2σv, n/2σd

Cnh

n = odd

E, Cn, σh, Sn

Cnh

n = even

E, Cn, σh, Sn, i

Dnh

Dnh

n = odd

n = even

Dnd

Dnd

n = odd

n = even

Sn

T

Th

Td

O

n = even only

Oh

I

Ih

Kh

E, Cn, σh, nC2, Sn, nσv

E, Cn, σh, n/2C2´, n/2┴C2´´, Sn, n/2σv,

n/2σd, i

E, Cn, nC2, i, S2n, nσd

E, Cn, nC2´, S2n, nd

E,

E,

E,

E,

E,

**Sn, Cn/2 and i if n/2 odd
**

4C3, 3C2

4C3, 3C2, 4S2n, i, 3h

4C3, 3C2, 3S4, 6d

3C4, 4C3, 6C2

E,

E,

E,

E,

**3C4, 4C3, 6C2, 4S6, 3S4, i, 3h, 6d
**

6C5, 10C3, 15C2

6C5, 10C3, 15C2, i, 6S10, 10S6, 15σ

infinite numbers of all symmetry

elements

Once you become more familiar with the symmetry elements and point groups described above,

you will find it quite straight forward to classify a molecule in terms of its point group. In the

mean time, the flowchart shown below provides a step-by-step approach to the problem.

Once you become more familiar with the symmetry elements and point groups described above,

you will find it quite straight forward to classify a molecule in terms of its point group. In the

mean time, the flowchart shown below provides a step-by-step approach to the problem.

1.4 Classification of Molecules into Point Groups

Procedure for Identification of Molecular Point Groups:Case 1:-The molecule is linear. In this case only two groups are possible: D∞h or C∞v. The

decision is easily made after ascertaining whether the molecule has or has not a centre

of symmetry.

Case 2:- The molecule has a regular geometry, suggesting type 3 symmetry group. In that case

we must identify more than one high order rotation axes Cn (n≥3). The Td group will be

indicated by four C3 axes, the 0h by three C4 axes and the Id by twelve C5 axes. . .

Case 3:- The low‐symmetry type of group is indicated by the presence of only one symmetry

element (Cn, σ or i). If the molecule has no symmetry elements, it belongs to the C1

**group. If it has only one rotation axis Cn, the Cn group must be considered. The
**

presence of only one reflection plane corresponds to the C3 group, and the identification

of only one inversion centre indicates the Ci group.

Case 4:- The molecule does not display the type 3 symmetry, but rotation axes are associated

with other symmetry elements. In that case the type 2 symmetry group is apparent. The

group is found by stepwise examination, in the following way:

Step 1:- The highest rotation axis has an even order. Determine if this proper rotation is

not associated with an improper rotation Sn of a higher order. If that is the case

and no other symmetry elements can be identified, group will be Sn'

Step 2:- The rotation axis is also associated with mirror planes. This may indicate the Cnv

group. To make sure, identify the n vertical mirror planes.

Step 3:- The rotation axis Cn; is perpendicular to the molecular plane. If that plane

contains no C2 axes, the Cnh group must be ascribed to the molecule.

Step 4:- If the rotation axis Cn is perpendicular to the molecular plane and this plane

contains nC2 axes, the molecule belongs to the Dnh group.

Step 5:-The molecule is not planar, but the C, axis is associated with nC2 axes

perpendicular to it. The Dn elements are present here. The Dnh group being

excluded (the molecule is not planar), look for diagonal planes, which indicate the

Dnd group.

START

A simpler approach:

**1.5Uses of point group symmetry and physical properties
**

Carrying out a symmetry operation on a molecule must not change any of its physical properties.

It turns out that this has some interesting consequences, allowing us to predict whether or not a

molecule may be chiral or polar on the basis of its point group.

1.5.1 Polarity

For a molecule to have a permanent dipole moment, it must have an asymmetric charge

distribution. The point group of the molecule not only determines whether the molecule may

have a dipole moment, but also in which direction(s) it may point.

If a molecule has a Cn axis with n>1, it cannot have a dipole moment perpendicular to the axis of

rotation (for example, a C2n rotation would interchange the ends of such a dipole moment and

reverse the polarity, which is not allowed – rotations with higher values of n would also change

the direction in which the dipole points). Any dipole must lie parallel to a Cn axis.

Also, if the point group of the molecule contains any symmetry operation that would interchange

the two ends of the molecule, such as σh mirror plane or a C2 rotation perpendicular to the

principal axis, then there cannot be a dipole moment along the axis. The only groups compatible

with a dipole moment are C2n, Cnv and Cs. In molecules belonging to Cn or Cnv the dipole

moment must lie along the axis of rotation is a polar molecule.

Therefore; a molecule cannot be polar if it has:

1. a center of inversion

–any group with i

2. an electric dipole moment perpendicular to any mirror planes

–any of the groups D and their derivatives

3. an electric dipole moment perpendicular toany axis of rotation

**4. –the cubic groups T, O, the icosahedral I, and their modifications
**

1.5.2 Chirality

One example of symmetry in chemistry that you will already have come across is found in the

isomeric pairs of molecules called enantiomers.

Enantiomers are non-superimposable mirror

**images of each other, and one consequence of this symmetrical relationship is that they rotate the
**

plane of polarised light passing through them in opposite directions. Such molecules are said to

be chiral*, meaning that they cannot be superimposed on their mirror image. Formally, the

symmetry element that precludes a molecule from being chiral is a rotation-reflection axis S.

Such an axis is often implied by other symmetry elements present in a group. For example; point

groups that have Cn and σh as elements will also have Sn. Similarly, a centre of inversion is

equivalent to S2. As a rule of thumb, a molecule definitely cannot have be chiral if it has a centre

of inversion or a mirror plane of any type (σh, σv or σd), but if these symmetry elements are

absent the molecule should be checked carefully for an Sn axis before it is assumed to be chiral.

Therefore; a molecule is not chiral if:

1. It possess an improper rotation axis S

2. It belongs to the group D

3. It belongs to Td or Oh

Summary of symmetry elements and their Matrix transformation:

- plane_frame.pdfUploaded bybobos
- conceptual foundations - the number system part 3Uploaded byapi-256719324
- Calculus for 2011Uploaded bykambly
- classicallaminationtheory-matlab program.pdfUploaded bypanbu
- G4 ProfilesUploaded byRenalTamP
- RotationUploaded byTikyo Jo
- Category PlotsUploaded byCharles Chandran
- Mech Intro2 14.0 L04 JointsUploaded bySebastian Lobos Opitz
- CHOICES 3 - C&C ManualUploaded byarindam_das
- EMC620S-Quiz2-2013.docUploaded byandrewzulu4455
- Unigraphics NX Sketching Fundamentals MT10028 (Student Guide)Uploaded bycyclotol
- Chem 120 Fall 2012 PS1 Answer Key(1)Uploaded bySteven Ly
- Modul Edit CoordinatesUploaded bysinar_ny
- Trial 2003 Admt P1Uploaded byRais Rahimi
- Laue & Bravis Crystal LatticeUploaded byVimal S. Katiyar
- Molecular dynamics simulation of dipole interactionsUploaded byDavid.R.Gilson
- MIT8_01SC_slides03Uploaded byAndrey Cabezas
- Translation & ReflectionUploaded byKugahn Aesen
- Robotics ReviewUploaded byvasudev1993
- Lecture 7Uploaded bySara El-Gendy
- module two ubd 2014 - completeUploaded byapi-257178130
- Sinumerik 810T 820T GA3 ProgrammingUploaded byNedret Bajramovic
- 13plus_mathssamplepaper2009_63369_1Uploaded byApachehc
- Burghardt 2005 Ica PcaUploaded byJayita Chakraborty
- 329003432-Synthetic-FFR-2.docxUploaded byash
- Grouped Frequency HistogramUploaded bytutorciecleteam
- eNGINEERUploaded byfilchibuff
- goc 2.pdfUploaded byvivek
- Jntu Anan 3 2 Me Cadcam Set 1Uploaded byAnuj Reddy
- Manual SmartBarsUploaded bycarloscatalan

- Instrumental Analysis Spectroscopy.ppt12Uploaded bykiya01
- IR Spectroscopu AmboUploaded bykiya01
- COUNCIL OF MINISTERS REGULATIONS TO PROVIDE FOR THE IMPLEMEN.pdfUploaded bykiya01
- Scientific CommunicationUploaded bykiya01
- Aspirin 2Uploaded bykiya01
- Spectroscopy Lecture noteUploaded bykiya01
- SaponificationUploaded bykiya01
- SpectroscopyUploaded bykiya01
- UV Vis ExercisesUploaded bykiya01
- Scientific Communication IIIUploaded bykiya01
- NMR MS Spectroscopy Ambo2 bUploaded bykiya01
- AChem NotesUploaded bykiya01
- Instrumental Analysis Spectroscopy.ppt12Uploaded bykiya01
- Introduction to Statistics for Chemistry - CopyUploaded bykiya01
- 411 Unit 3FUploaded bykiya01
- Research Methodology,12Uploaded bykiya01
- Exercises For spectroscopic techniques-Ambo 2012.docxUploaded bykiya01
- Research Methodology,12Uploaded bykiya01
- Module 4Uploaded bykiya01
- Research Methodology,12Uploaded bykiya01
- Research Methodology,Uploaded bykiya01
- Schrodinger Eq nUploaded bykiya01
- Research Methodology,12Uploaded bykiya01
- kaizeneUploaded bykiya01
- Agreement FormUploaded bykiya01
- BookUploaded bykiya01
- 04 KZN BG Form Process 5S Evaluation Sheet(Sample)Uploaded bykiya01
- Agreement FormUploaded bykiya01
- 04 KZN BG Form Process 5S Evaluation Sheet(Sample)Uploaded bykiya01