136 PART-B 11. Discuss the law of photochemical equivalence. Why the ‘equanium yield values ae'very high for certain resetions? 12, Define and explain quantium yield af a photockernia! reaction 13, Giving Jabionsky diagram, explain the varions reaiaive and nog - radiative processes 14, Discuss photoseesitization 15, Bring ont he dffereaces between primary and secondary processes in a photochemical reaction 16, Distinguish between thermal and photochemical reactions 17. Drawing Jablonski diagram, explain the transitions Snvolved in phosphorescence ate Grothus - Drapper law and Stark - Einstein aw 15, PART-C 19. WithneatJeborsk diagrams, explain uorescence and phosphorescence Whotisanactinometer? Deseibehow a uranyl oxalate ssinometr may bese 20.) Tokina -Cl wactionasan exam, npn tbe pirat corsa process photochemical action 4 Wie trietly cui phaosrsitston &ROUP THEORY IAL SYMMETRY ELEMENTS AND SYMMETRY OPERATIONS Symmetey elements 2 yey lens: pameta eniy sch sean neo poi seu cha yay done, ae Spmmotry operations A symmetry operation is a movement of a body (ivolecule} such that the resulting configuration ef the rmalecule is indistinguish le from the eriginal. The resulting configuration may be an equivalent or tential configuration, Bs inte Consider H, molecule of configuration I. It can be rotated by 180" to give an eguivalent configuration I Application of the rotation operation twice produces an identical configuration HL ao! 1a ne, Py a Pa, 12m f aymmetry chem Hy re of symmetey (a) : It js an imaginary plane within the motecule which divides it into two halves, fone is the mirror image of the other. If reflection of any atom of the molecule is carried out on the plane of symmetry. it coincidences with another equivalent stom Thus, the plane of symmetty is nothing but a reftection plane, The reflection planes can be classified into three types based on their relation with the principal axis, i) A plane is referred to as horizontal plane (0,) if it & perpendicular to the principal axis. yas iH) A reflection plane drawn vertically through the principal axis sealed vertical plane (o,). For pe wate molecule eee, pli. shich apne sven "though the pris axis conning fy Orton aed being + boeberweethe Cit 202 108) A vertical plate which hiseets two perpendicular ( ves is called a dihedral plone 6,1 C, ais 2 Proper axis of symmetry (C,) : It is an imaginary line passing through the molecule about which rotaion -can be cartied to attain an equivalent configuration, (2 eneral, the symbol for proper axis of symmetty is C, here n is known as the order of the axis. It is given by the formats 360 nao where 0 is the minimum angle of rotation to obtain the cauivalent configuration. The proper axis of symmetry is merely a rotation axis, Exomples 4) Water molecule is rotated by an angle of 180° about 47 aris (o get an equivalent or identical contiguraion, Now, the order of the axis is 2 and the axis is knowa, 45.C, axis of symmetryii) Boron trichloride molecule has the C, axis of symmetry. The minisum angle of rotation (0) to obtain the equivalent configuration is 120" ut cr cl jon has 8 C, axis of symmetry. ‘The oe ‘ion is obtained by rotating the ion ‘equivalent configurat through 90° about this axis. Cais a > ee rc am [ 205 iv) Benzene molecule hat 3 C, nis of symmetry Cats w etry (S,): It is am imaginary line passiog through the molecule about which rotation followed by reflection in a ‘rotation axis can be performed to attain an equivalent configuration. Thus, ar improper axis of symmetry is 4 rolation-reflection aris, Trans-dicbloroethylene provides an example of molecule with $, axis of symmetry, This molecule possesses C, axis and-o, plane. MK co Gee Co ten Nag teal 2 ioe Y= wa oe Vs WON 4. Centre of symmetry (I) : This is 2 point such that «any line drawa through it meets the same atom at equal distances in opposite directions. Thus, the centre of symmetty is a centre of inversion. Examples oy /| | H ! | 2.06 iio, iii) CHCl, a HW . < ( % 5. Identity ‘A-symmetry operation which brings back lhe molecule 10 the original orientation (configuration) is called identity ‘operation . This is the operation of doing nothing (leaving the molecule unchanged). The corresponding symmetry clement is called the identy, whichis denoted as (from the Germam ‘word Einheir meaning unity). All molecules possess identity ‘Symmetry elements and operation [Symmetry element Plane of Reflectionin a plane symmetry (4) perpendicular to the Principal axis, 2, Plane of Refleetionin a plane symmetry (o,) | coniaining the pet 207 Reflection ina plane which bisects two perpendicular C,axis of symmetry 3.Planeof symmetry (04) f Rotation by an angle © =(28/n) about the axis AProper symmetey (C,) xotation by an angle 0=(2x/n) bout an axis followed by reflection ina plane perpendicular to the rotation axis S.Amproper axis of symmetry (S,) 6. Centre of Inversion of all atoms through symmetry (i) point 7. Idendity (E) This operation leaves the molecule unchanged Products of symmetry operations Let X and Y be two symmetry operations. Suppose operation X is carried out first and then operation Y fiiving the same net effect when a single operation Z is carried out, This we express symbolically as YX = Z That is, the effect produced by operation Z is the product of the effects produced by the successive operations X and Y,1.08 angles to one another, there must necessarily be w third at right angles to both. Suppose that the two given axes coincide with the x and y axes; we can designate them C(X1 and C,(¥). On applying first CCK) and then CACY) to a general point, the following transformations ‘of its coordinates take place cea. cu, bey Yo 2) bay Yo Ad day te wae of bite sea 45h th ale of, Bela aca fee Tabu we aly Ce neeal poral, it As shifted to [-%,. ye ty): Thus, 8 may write ; CAV) CX) = 2) ‘Thus, whenever C\(X) and C,(Y) exists, C,(Z) must aise cast, because it is their product General relations among symmetry operations 1. The product of two proper rotations must be a pploper rotation, CX) 6,0) = C2) 2, -The product of two reflections, tm planes A and B intersecting at an angle 0 is 3 rotation by 20 about the anis defined by the line of intersection, rotations about axes which inet rotation by 20 about an anis intersect at an angle @ is 2 y perpendicular to the plane of the C, axes. Let X and ¥ be two symmetry product equals to Z. Commutation rule + operations and their 2.09 YX =2 When the result of the sequence XY is the same as the feault of the sequence YX, the two operations X and ¥ are said to commute. This is called commutation rule, The following pairs of operations always commute |, Two rotations about the same axis Reflections through planes perpendicul lber 3. The 4. Two C, sotations about perpendicular axes 5. Rotation and reflection in a plane perpendicular to the rotation axis. to each In and any reflection oF rotation. sub-groups and Groups ‘A group is a collection of symmetry elements which sre inter-related according to certain rules. Groups may be either finite or infinite, that is, they may contain a limited oF an untimited number of elements. The symmetry soups are mostly finite. The number of elements in a finite group is called its order and the conventional ‘symbol for the order is A. A group in which all elements commute is called an Abelian group. In an Abelian group the order of addition is immateti Conditions for the symmetry elements to form a mathematical group 1, TwoelementsA and B ofa group combine to give the third element C of the proup2.10 ABEC 2. Alelement combines itself to form another element of the group. M=B . Every element of the group obeys the rommutation law. Element Aand B aresaid to commute when AB=BA 4. The group must cantain the identity element , E which commutes with all the elements and leaves them unchanged 5. Every element of the group obeys the association law of combination. If A,B and C are three clements of the group, then (AB)C =A(BC) 6. Every clement(A) of a group has an inverse or reciprocal (A") combine to give the identity element ! AMM=ATATE Types of Groups 1. Finkte group : A group containing i finite or limited number of elements is called ® finite group. The symmetry groups with which we shall be concerned are mosily finite. The number of elements in a finite group 24 's called its order and is represented as A. In a point Broup, order is the number of symmetry operations possible. Thus, in C,, group, order is 4 and in C,,, order is 6. 2. Infinite group = A group containing infinite or unlimited number of elements is ealled an infinite Sroup. Linear molecules belong to this group. 4. Abellan group : A group in which all the elements commite is called an Abelian group. Two elements A and B’ commute if AB = BA. The set of numbers between -¢ and +e form an Abelian group under the multiplic n process. The set of symmetry operations ‘of water molecule represents an Abelian group since Ithey obey the commutative law 4. Non-Abelian group : A group is said to be non- Abelian if all the elements do.not commute with one another. The symmetry operations of the ammonis molecule provide an example for the non-Abelian group. The elements of the group viz. E, C,', C, cy 6,1 and 9," do not obey the commutative law. 5. Cyelic group : A group is said to be cyclic if all the elements of @ group can be generated ftom one element. A, A}, A... AY form the elements of a cytlie group with A* as the identity element, Here, to the total number of elements an: n refers called the order of the group. Hydrogen peroxide is an example of molecule which possesses symmetry operations” corresponding to & cyclic group,\ ao) 1p Multiplication Table ‘The elements of a group can be Hsted in a table Known as the group multiplication table, This table reveals the different relations between the elements of «group. The multiplication table consists of m row a ‘n columns. Each column is labelled with a group” ‘element and so is each row The entry in the table under a given column and along a given row is the product of the elements which head that column and that row. Thus, at the intersection of the column labelled by x and the row labelled by y we find the element which is the product ay. The group multiplication table for water molecule is given below E G ¢, ° E E c «, 0 cg |G E 0, 9, e | 9, o! E c o | of 6, C, E ‘An important theorem about group multiplication table is the rearrangement theorem, According to this theorem, each row and each column in the group multiplication table lists each of the group elements once and only once. From this, it follows that no two rows may be identical nor may any two columns be identical. Thus, each row and each column is a rearranged list of the group elements. 20 Sub groups : ‘Smaller groups which may be found within a larger ‘grou0 ate called sub groups, The elements of a subgroup should obey the following cunditions : |. The elements should satisfy all the rules of the group. 2. It g is the order of the group and s is the order of the subgroup, then g/s is a positive integer other than E10. Exampes : The subgroups in water molecule can be identified using the group multiplic siven. They are as folows : LE 2. E and C, 3. E and 0, 4, E and 6 Classes A complete set of elements which are conjugate to fone another is ealled a class of the group. Conjugate elements are related by the equation, X"AX = B where X is another element of the group. X is known as the similarity transformation element. The similarity tansformation of one element by another may be used to find whether 2 set of elements form a class. For example, water molecule has four symmetry operations Viz. E, Cy 6, 0,', The similarity transform of 3 Parlicular operation is obtained with all the operations as follows :- 24 B'GE = ¢, o'C,o, = ¢, (,)" C, o'= C, . C'C¢, = ¢, The element in a class should satisfy the following condition : The order.of a class must be an integral factor of the order of the group. 1B] POINT GROUPS ‘ All the symmetry operations present in a molcule form a group, A groun is generally called point group since all the elements of symmetry present in the melecule intersect at a common poiat and this point remains fixed under all the symmetry operations of the molecule. The point groups of molecules are denoted by specific symbols. Classification of point groups 1. C,, point groups ‘A molecule which possesses the identity element (E), proper axis of symmetry (C,) and n vertical planes of symmetry (6,) belongs to C,, point group. ¥ C,, point group + (c.g. Water) Water belongs to C,, point group which contains four symmetry operations - E, C, and 20, a) The molecule has 2 two-fold (C,) axis of symmetry 218 which passes through O-atom and in betwzen the two - Heatoms. b) The motecule has two vertical o, planes. One is the molecular plane Gyaxis containing O and H- atoms and the other is passing through the C, axis 4° to the molecular plane (i.e through O-atom and between two H-atoms, , plane 9; plane 1-C,, point group : (e.g. Ammonia) ‘Ammonia belongs to C,, point group which consists of six symmetry operations - E, 2C, and 3o,. 4) The axis passing through N-atom and the centre of the triangle containing three H-atoms is a three-fold (C,) axis. Garis nao fa a 4) There are three ©, planes each passing through N- atom and one of the H-atoms. They are designated ts ©, 0, and 6,"216 [> 2. Cy point groups If a molecule has the identity element (E), proper axis of symmetry (C,) and a horizontal plane (0), it is assigned the point group C,, The inversion centre , (i) is also present is this point group if the order of ~. the C, axis is even, 1) Cy point group + (e.g. Trans-dichloroethylens) 7 : ‘This point group consists of four symmetry operations: E, Cy o, and i. 8). The molecule has 1 centre of symmetry (inversion centre, i) . b) There is a two-fold axis of symmetry (C;) perpendicular to the moteculsr plane. This molesvlar plane passing through the Ch and H-atoms is the - horizontal 0, plane. 3. Dy polat gro . The point group with the principal C, axis, m ‘perpendicular C, axes and a horizontal o, plane is designated as D,, group. Such » group will naturally * have vertical a, planes too, ~ ‘This group possesses the inversion centre when the C, axis is of even order. Y Dy, point group : (e.g. Trans-dichlorodiamine Ni (11) The D,, point group has 8 symmetcy operations - E, 3C,, 20,, 0, and i a) There are three C, axes of symmetry, one passing through the Clatoms, another passing through the NH, groups and the third is 4! to the plane of the molecule, ) There are two a, planes and one ©, plane, ©) There is an inversion centre ) at the metal ion218 ‘ 9, plane C,axis g plane Fo. plane W) Dy point group : (e.g. BF.) BF, has a trigonal planar structure. The point group of the molecule is D,,. It has 12 symmetry operations E, 2C,, 28,, 3€,, 30, and 0, 8) The principal axis perpendicular to the plan of the molecule is C, It is a three - field axis passing through the centrel B - atom.,Desides the C, axis, there are three subsidiary C, axes, passing through B - atom and each of the F = atom b) There are three vertical planes (0,) and horizontal plane (6,) in the molecule g,plane Cyaxis gone plane UW) D,, point group : N)) ‘The square planner [Ni(CN),}* ion belongs to Dh point group. It has 16 symmetry operations: 219 E, 3C, AC, 28, 40, 6, and i 8) The axis passing through Ni and perpendicular to the Plane is an axis of four-fold symmetry (C,). Besides the C, axis, there are four C, axes of symmetry, b) There are four o, planes and one 9, plane, An inversion centre is also there. We) D,, point group + (e.g. Benzene) Benzene moleule comes under the point group Dy has 24 symmetry operations : E, Sy, 6Cy 28, 28, 60,, 0, and i 8) The principal C, axis passés through the centre of the hexayonal ring (inversion centre) and perpendicular to the plane of the rine, Besides the six-fold axes ofae 20 . symimefiy. there ate sie C, anes of symmetry! three passing’ symmetty nd 140 opposite (Calor and thrce pasuing thtough the centre of ymmmetty and centres of two opposite edges ough the eens b) There are six 0, planes, thee passing. through opposite C-atoms and thice passing through the centres of the two opposite cdges. The plane passing through six Ceatoms and is perpendicular to C, axis is the plane. ~ ¥) Day Polat group: (eg. CO) ; CO, is a linear molecule with: ‘a centre of symmetry. It haste det element (EC, ax « perpendicular Cy fo, and o, lanes. It belongs to Day point group an Se aymmenyclemenis:E,2Ce, 091 Sys! 28= end = Cy- 4) Tetrahedral or 1, Polat grou i) SF, (e4,SEyCH) ‘The tetrahedral SiF, molecule belongs to the T, Point group. It has 24 symmetry operations : E, 8C,, 3C, 65, & 60, 4) There are four axes of three-fold symmetry (C,) cach passing through the Si-alom, one H-atom and the centre of the opposite face. b) There are three axes of two-fold symmetry (C,) each Passing through the centres of two opposite edges22 ©) Each of the C, axis is also S, 4) There are six a, planes each passing through ang « tdee and the cenlres of the opposite edges. i cH, S. Octahedral or O, point group : (c.g. SF,) The octahedral SF, molecule comes under the O,. point group. I has 48 symmetry operations : E,BCy 6C,, 6Cy ICK=C,'), i, 68, 88, 30,, and 60, c F RK 4) There are three C, axes of symmetry passing through toms at the opposite comers. The C, axes are two coincident with three S, axes. 20 b) There are four C, axes of symmetty passing through four paits of opposite irigonal faces. They are coincident with four S, axes, ©) There are six C, axes of symmetry, each bisects opposite edges : ) The molecule has 30, planes passing through four corners and 60, planes pissing through F, Fy. Fy F, is © 0, plane. The plane passing through F, and F, comers and centres of edges FF, and F,F, is 6, ©) There is also an inversion centre in the molecule, Exercises (A Prove that C,,(e.g.,0 molecule) Is group. Abelian Proof : The C,, group consists of four symmetry operations - E, C,, a, and o/. © a 6 oe JN ON DP A Oh nH From the above figure, Cx 0,=0,xC, (C, operation followed by a, gives the same result as 4G, followed by C, operation), Similarly, Cx of =o) xc,224 Thus, all the elements present im C,, group are commutable, That is, C,, is an Abelian group. Brrrove that ©, (een, ‘group. Aommonis belongs to C,, group. This group contains 6 symmetry operations - E, 2C,, 0,0,’ and 9". From the above figure, we found that Gx All the elements present in the group donot commute with each other. Therefore, C,, is not an Abelian group. ecules Group theory and Chirality of motec "s molecule is chiral if it has no emt vie. atis of symmetry (S,) centre of symmenry (i) and plane of symmetry (0)- Beompls 1 ciFcivisekalesiiesngtenet ofS i vertical planes 2. NH, ismot chiral as ithas thee vert 43, CH= C=CH,(allene) isnot chiral es it hasan Nea) eC, 225 QUESTIONS PART -A 4. Tho symbol for proper aus of rolation is as, DE ga ac, 2. HO molecule belongs (otha point group aC, )D, ye, 0, 3. [ICL]? belongs to the point group aC, HD, wyT, 4. In general he rats of the equation X* 1 = O ora 8) Cyclic group ) Sub group ©} Non abelian group d) None of these 5, The point group with no centre cl inversion is 1D, OD, dT, gy, §.Amelecules notchial dithas 8) plane of symmetry b) axis ef symmety Sleente of symmetry d)altof these are coneet 7. SF, molecu befangs tothe pont group 3D, 81, go, oD, 8. Rotation retexion axis present in HO —b)NH, §—@)BF, date above 8. Which of he folowing is not rue? aC, x0,=€ 21C,Xa,20, ea,xE=a, d)0,x0,2E 10.C,, point group is assigned to 4)H,0 0/60, BF, wCH,