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Molecular Symmetry Symmetry Elements Symmetry Operations Point Groups Largely taken from Martin Poliakoff’s notes

MOLECULAR SYMMETRY

Know intuitively what "symmetry" means - how to make it quantitative?

Will stick to isolated, finite molecules (not crystals). SYMMETRY OPERATION

Carry out some operation on a molecule (or other object) - e.g. rotation. If final configuration is INDISTINGUISHABLE from the initial one - then the operation is a SYMMETRY OPERATION for that object. The line, point, or plane about which the operation occurs is a SYMMETRY ELEMENT

N.B. “Indistinguishable” does not necessarily mean “identical”.

e.g. for a square piece of card, rotate by 90º as shown below:

1

2

4

1

90o

4 3

rotation

3

2

**i.e. the operation of rotating by 90o is a symmetry operation for this object
**

Labels show final configuration is NOT identical to original. Further 90º rotations give other indistinguishable configurations - until after 4 (360º) the result is identical.

see below) which convert molecule into configuration indistinguishable from original. reflections. PLANE or POINT about which the symmetry operation is performed. element was a ROTATION AXIS. Example above operation was rotation. SYMMETRY ELEMENTS Each element is a LINE. .SYMMETRY OPERATIONS Motions of molecule (rotations. . inversions etc. Other examples later.

/reflection axis)Sn1.Snn-1 (n even) (rot.) E (identity) Cn1...Cnn-1 (rotation about axis) σ (reflection in plane) i (inversion at centre) Sn1..Summary of symmetry elements and operations: Symmetry element Symmetry operation(s) – Cn (rotation axis) σ (reflection plane) i (centre of symm..../reflection about axis) ...Sn2n-1 (n odd) Sn (rot.

Notes (i) symmetry operations more fundamental. (ii) some symmetry elements give rise to more than one operation . bisecting HOH angle is a rotation axis.AXES OF SYMMETRY Some examples for different types of molecule: e.as above.especially rotation . but elements often easier to spot. giving indistinguishable configuration on rotation by 180o.g. ROTATIONS . H2O rotate O (1)H H(2) 180 o O (2)H H(1) Line in molecular plane. .

Take as axis a line perpendicular to molecular plane. F(3) F(1) 120o B (2)F F(3) B (1)F axis perpendicular to plane F(2) view down here N. (1)F B z F(3) F(2) . planar. all rotations CLOCKWISE when viewed along -z direction.BF3 By VSEPR .B.trigonal. passing through B atom. all bonds equal. all angles 120o.

e. One axis can give rise to >1 rotation.Symbol for axes of symmetry Cn where rotation about axis gives indistinguishable configuration every (360/n)o (i. 1 Rotation by 120o described as C3 . what if we rotate by 240o? F(3) B (1)F F(2) 240o (3)F F(2) B F(1) Must differentiate between two operations. . for BF3. an n-fold axis) Thus H2O has a C2 (two-fold) axis.g. BF3 a C3 (three-fold) axis. e. 2 rotation by 240o as C3 .

Rotation by 360o is exactly equivalent to rotation by 0o.. . the operation of doing NOTHING to the molecule. which introduces a new type of symmetry operation.. C22 and for BF3 C33 both bring the molecule to an IDENTICAL arrangement to initial one.In general Cn axis (minimum angle of rotation (360/n)o) gives operations Cnm. IDENTITY OPERATION For H2O.. where both m and n are integers.. i. When m = n we have a special case.e.

MORE ROTATION AXES xenon tetrafluoride. C5H5 H(1) (5)H C C C (4)H C5 H(2) – H(5) . XeF4 C4 (4)F F(1) Xe F(3) F(2) (3)F F(4) Xe F(2) F(1) 90 o cyclopentadienide ion. C C (4)H C C C C C H(1) 72 H(3) o (3)H H(2) .

benzene. Examples also known of C7 and C8 axes. . C6H6 H(1) (6)H C C (5)H C6 C H(4) C H(2) C C H(3) 60o (4)H (5)H C C C H(3) H(6) C C C H(2) H(1) .

and the operations generated by C6 are: C61. C65. C64 (C32).e. even order) present. C44 (E) Similarly. a C6 axis is accompanied by C3 and C2. C63 (C21).e.e. C66 (E) . then Cn must also be present: C4 (4)F F(1) Xe F(3) i. C43. and the operations generated by C4 can be written: C41. C62 (C31). C42 (≡ C21) 180 o F(4) F(2) 90 i. C41 o (3)F Xe F(2) F(3) F(1) (2)F Xe F(4) F(1) Therefore there must be a C2 axis coincident with C4. C42 (C21).If a C2n axis (i.

one along each B-F bond. e. perpendicular to C3 .Molecules can possess several distinct axes.g. BF3: F C3 F B F C2 C2 C2 Three C2 axes.

e. Therefore any plane containing this axis is a VERTICAL PLANE.Operation = reflection symbol σ Element = plane of symmetry Greek letter ‘sigma’ Several different types of symmetry plane different orientations with respect to symmetry axes. By convention . σv.g. H2O plane above (often also called σ(xz)) Can be >1 vertical plane. e. for H2O there is also: .g.highest order rotation axis drawn VERTICAL.

σh. therefore symmetry plane This is also a vertical plane.z O (1)H x H(2) y σ(yz) .g. e. to C4) is a symmetry plane. for XeF4: C4 F Xe F F F Plane of molecule (perp. σh) .e.reflection leaves all atoms unshifted. Any symmetry plane PERPENDICULAR to main axis is a HORIZONTAL PLANE. but symmetrically different from other. i. could be labelled σv'.

F Two final points about planes of symmetry: (i) if no Cn axis. (ii) unlike rotations.Some molecules possess additional planes. i.e. but not always.but two different from others.i. which need a separate label.Those along bonds called σv. A second reflection returns you to original state.g. e. (σ)(σ) = σ2 = E . plane just called σ. but those bisecting bonds σd . only ONE operation per plane. σv and σd differentiated in same way.e. DIHEDRAL PLANES Usually. XeF4 σv σd σv F F Xe F σd Four "vertical" planes . as well as σv and σh.

-z). 0. -z) . z inversion y (-x.z) to (-x. y.y. z) x The origin. OPERATION : INVERSION ELEMENT : a POINT .CENTRE OF SYMMETRY or INVERSION CENTRE. -y. x (x.e. and the resulting arrangement is indistinguishable from original .the INVERSION is a symmetry operation. If the coordinates of every point are changed from (x.INVERSION : CENTRES OF SYMMETRY Best described in terms of cartesian axes: Involves BOTH rotation AND reflection. 0) is the centre of inversion. z y . (0. -y. and the molecule possesses a CENTRE OF SYMMETRY (INVERSION) (i. CENTROSYMMETRIC) .

trans-N2F2 F(2) (1)N (1)F F(1) inversion (2)N (2)F N(1) .and out the same distance in the same direction on the other side.g.same for operation (inversion) and element (centre): i Another example: XeF4 F(1) F(3) i (4)F Xe F(2) (2)F Xe F(4) F(3) Xe atom is centre of symmetry F(1) . inversion involves taking every atom to the centre . N(2) centre of symmetry In practice.e. Symbol .

-y. the presence of a centre of symmetry only generates one new operation. y. (x. z) Follow this by reflection in the xy plane (-x. -y. y.e. z) i (-x. -z) i (x.As for reflections. -y. -z) (-x. y. (i)(i) = i2 = E Inversion is a COMPOSITE operation. z) (-x. since carrying out inversion twice returns everything back to start. -y. z) . z) i. with both rotation and reflection components. Consider a rotation by 180o about the z axis: (x.

BUT individual components need not be symmetry operations themselves..g. of rotation by 180o or reflection in a plane perpendicular to the axis. then inversion (i) must also be a symmetry operation.. however... a molecule does possess a C2 axis and a σh (perpendicular) plane as symmetry operations.. If.. do not.... .. Inversion at centre gives indistinguishable configuration. staggered conformation of CHClBr-CHClBr H C Cl Br centre Br Cl . e... C H The components.

IMPROPER ROTATIONS : ROTATION-REFLECTION AXES Operation: clockwise rotation (viewed along -z direction) followed by reflection in a plane perpendicular to that axis. Element: rotation-reflection axis (sometimes known as "alternating axis of symmetry") As for inversion . .components need not be themselves symmetry operations for the molecule.

e. a regular tetrahedral molecule. such as CH4 H C H H H rotate 90 o H H C H H reflect H C four-fold rotation reflection S41 Symbols: rotation-reflection axis rotation-reflection H H H Sn (element) Snm (operations) where rotation is through (360/n)o .g.

σh separately. Ethane in staggered conformation H H H i.g.e.trigonal planar C3. rotate by 60o and reflect in perp. S3 F B F F σh in plane of molecule.there must also be an Sn axis : e. therefore S5 also. therefore S31 must also be a symmetry operation Other Sn examples: IF7. Note NO C6.S4 axis requires presence of coincident C2 axis If Cn and σh are both present individually . has C5 and σh. C31 + σh individually. BF3 . plane. C H H C H S6 . pentagonal bipyramid.

molecule belongs to point group Cs .if one is found.POINT GROUPS A collection of symmetry operations all of which pass through a single point A point group for a molecule is a quantitative measure of the symmetry of that molecule ASSIGNMENT OF MOLECULES TO POINT GROUPS STEP 1 : LOOK FOR AN AXIS OF SYMMETRY If one is found .go to STEP 2 If not: look for (a) plane of symmetry .

if one is found.POINT GROUPS A collection of symmetry operations all of which pass through a single point A point group for a molecule is a quantitative measure of the symmetry of that molecule ASSIGNMENT OF MOLECULES TO POINT GROUPS STEP 1 : LOOK FOR AN AXIS OF SYMMETRY If one is found . molecule belongs to point group Cs .go to STEP 2 If not: look for (a) plane of symmetry .

F Cl . Hence Cs point group. No axes. plane or centre. H C Cl Br C Br Cl No axis. S O Cl Cl No axis.. CHFClBr No symmetry except E.g. look for (b) centre of symmetry . therefore (c) no symmetry except E : point group C1 rotation through 360o) H e. O. no planes. H (so called because E = C1. therefore point C Br group C1. molecule belongs to point group e.e. CHClBrCHClBr (staggered conformation): Ci.if one is found. but mid-point of C-C bond is centre of symmetry. but plane containing S. bisecting ClSCl angle. is a symmetry plane.g. If no plane is found. SOCl2 . Therefore Ci point group.g.

trans-N2F2: N F . through mid-pt. σh). N molecular plane is plane of symmetry (perp. of N=N bond). to plane. If found. if found . look for (a) a HORIZONTAL PLANE OF SYMMETRY.e.STEP 2 : LOOK FOR C2 AXES PERPENDICULAR TO Cn If found. If there is no horizontal plane. molecule belongs to point group Cnv . but F e. If not.g. look for (b) n VERTICAL PLANES OF SYMMETRY. No C2 axes perp. to C2. to this. i. go to STEP 3.point group is (Cn = highest order axis) Cnh Highest order axis is C2 (perp. Point group C2h.

Many examples. each contains P. one Cl Therefore C3v BrF5 By VSEPR. Point group C2v PCl3 P Cl C3 Cl Cl C3 highest order axis No C2's perp. to C4 No σh.g. H2O C2 axis as shown. but 4 vertical planes. one perp. e. square pyramidal Highest order axis : C4 F F F C4 Br F F No C2's perp. to C3 No σh. but 3 σv's. No other C2's. no O H C2 H σh. Therefore C4v . one in plane. bisecting HOH angle. to plane. but two sv's.

B. or (d) an S2n axis coincident with Cn: point group S2n . two are σv's. could have (c) no other symmetry elements: point group Cn . of 4 vertical planes. two σd's σv σd σv F F Br F (looking down C4 axis) F σd If no planes at all.N.

to Cn.plane of molecule . point group is e. to C3 C2 σh .g. If present.along C=C bond C2 C H Two additional C2's as shown. C2H4 Dnh C2 H C C2 H H Highest order axis C2 .STEP 3 If there are nC2's perp. ethene (ethylene). look for: (a) horizontal plane of symmetry. σh in plane defined by the last two C2's Point group D2h BF3 Planar trigonal molecule by VSEPR C3 F C2 B F F C2 Main axis C3 Point group D3h 3 C2's perp.

If these are present.XeF4 Square planar by VSEPR C4 C2" F F C2" F Xe F Main axis C4 C2' 4 C2's perp.plane of molecule C2' Point group D4h If no σh. molecule belongs to point group Dnd . 2 bisecting. look for: (b) n vertical planes of symmetry (σv/σd). to C4 (2 along XeF bonds (C2'). (C2")) σh .

.each containing one CH2 unit Point group D2d A few molecules do not appear to fit into this general scheme.... .. H C H C C H H C2 (main axis) H Looking down C=C=C bond C2' H C2' H C H Main axis C2 ..g.. H2C=C=CH2..along C=C=C Two C2's as shown Two vertical planes (σd) . allene.e..

so infinite number of rotations. Molecular axis is C∞ . Also any plane containing axis is symmetry plane. e. so infinite number of planes of symmetry. but ∞ σv's containing main axis: point group C ∞v .g.: H C N C∞ No C2's perp. Divide linear molecules into two groups: (i) No centre of symmetry.LINEAR MOLECULES Do in fact fit into scheme .but they have an infinite number of symmetry operations.rotation by any arbitrary angle (360/∞)o. to main axis.

highest order axes.g. C∞ + ∞C2's + σh Point group D∞h Highly symmetrical molecules A few geometries have several.(ii) Centre of symmetry.: C2 O σh C O C∞ C2 i. Two geometries most important: . equivalent.e. e.

Regular tetrahedron e. several planes.g. F F S F F F F 3C4's (along F-S-F axes) also 4 C3's. . S4. and a centre of symmetry (at S atom) Point group Oh These molecules can be identified without going through the usual steps. Note: many of the more symmetrical molecules possess many more symmetry operations than are needed to assign the point group.g. 6 C2's. Cl Si Cl Cl Cl 4 C3 axes (one along each bond) 3 C2 axes (bisecting pairs of bonds) 3 S4 axes (coincident with C2's) 6 σd's (each containing Si and 2 Cl's) Point group: Td Regular octahedron e. S6 axes.

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