SYMMETRY, GROUP THEORY AND THEIR APPLICATIONS 1) Symmetry elements and operations A symmetry element is a geometrical object such as a point, line or plane with respect to which some particular symmetry operation(s) can be carried out. A symmetry operation is a movement of a species such that after it is complete, the original and the product of this movement are undistinguishable. Generated by a symmetry element. Symmetry element & its symbol How the related symmetry operation works Identity, E (y.2) > yz) Center of symmetry, / (%y2) > (XrY-2) Mirror plane, « (case of oy) (y.2) > Kyr2) Proper rotational axis, C,, (z axis) (Xy.2)>(xcosa-ysina,xsinatycosa,z); a=2ma/n Improper rotational axis, S, (z axis) (xy,2)>(xcosa-ysina, xsina+ycosa,-2); a=2mn/n Relatnships between 8," and oer symmetry operations 8,=0; 8,2"=C,2"(n24) 2) Molecules with symmetry elements E and i, , C, and S, Symmetry operation € leaves each point on is place: 41) Symmetry element: identity, (xyz) > (xyz) € 2) Symmetry elements: E and center of inversion, i. i c ‘Symmetry operation i moves all atoms through the center: e (Ky.2) > (K-¥-2) © 3) Symmetry elements: E and mirror plane, 0. ‘Symmetry operation o,y moves all atoms through the plane xy: yz) > (6yez) 4) Symmetry elements: E and proper axis, C2. ‘Symi ety opens C," rotate atoms about the axis 160/2) degrees (1 m <2) 5) Symmetry elements: E, C,, Cy, 6, Improper axis, 8, _Symety opezaons Sy" roa aloms about he axis by 3604 degrees and then reflect in a perpendicular mirror plane. This Sequence is repeated m times (t's m= 4)3) Groups Using four rules defined below, certain sets of symmetry epetans (symmetry operations are designated below as A, A“, B, C, E) can be combined into symmetry point groups. 1) The combination (multiplication) of any two operations of the group, A & B, is another operation C which belongs to the group: AB = C 2) One of the operations in the group must commute with all others and leave them unchanged: EA = AE = A. This operation is identity, E. 3) The associative law must hold: A(BC) = (AB)C 4) Each operation A must have a reciprocal A‘ which is also an operation of the group; A A‘ = E Conclusion: identity operation, E, is present in each symmetry point group 4) Group multiplication tables. Point groups of low symmetry + Multiplication table for each symmetry point group contains columns and rows labeled with symbols of all symmetry operations present in the group. The products of the symmetry operations are indicated at the intersections (see examples below). + Each row and each column of the table lists each of the group operations ‘ach row only once. Thus, no two rows or two columns must be identi and each column is a rearranged list of the group oper Three Point Groups of low symmetry: rte % oe G, E E E qamm maa m5) Point groups with n-fold rotational axis €, : rotational axes only; no mirror planes C,~gauche-H,0, (operations: E, C,) Cin: a horizontal plane perpendicular to C,, is present Cy ~ trans-HN=NH (operations: E, C,, i, c) Cy : vertical plane(s) containing C,,is(are) present Cs, — NH, (operations: E, C,', C:2, 36,) C,, : infinite number of vertical planes containing C,, linear molecules without center of symmetry: CO, HF, N,O (operations: E, 2C;., *c,) ¢ 6) Dihedral groups Contain nC, axes perpendicular to the principal axis C,, D, : no mirror planes 1D; -Co(en),°* (operations: E, 2C;, 3C,) Dy -CH,=CH, (operations: E, 3C,,, i, 30) Dj, - PCI; (operations: E, 2C,, 3C,, c,, 283, 36,) Day PICL? Dy: infinite number of nC, axes linear centrosymmetrical molecules like H, CO, etc D4: mirror planes contain C, and bisect the angle formed with adjacent C, axes D,4-ethane/staggered Du Ss Dy Cr(CcHg)a © Da mirror plane perpendicular to the principal axis7) Point Groups with improper axes S,, (n 2 2) 1,3,5,7-tetrafluorocycloocta-1,3,5,7-tetraene (S,), [6.5]-coronane (S,) Se Symmetry elements: E, S,,C, E, Cy, i, Ss Special cases: S, =o, S, 8) Point Groups of high symmetry (cubic groups) In contrast to groups C, D, and S, cubic symmetry groups are characterized by the presence of severai rotational axes of high order (= 3). Cases of regular polyhedra: + Ty (tetrahedral) BF, , CH, | i in F F Symmetry elements: E, 4C;, 3C;, 35,, 60, ‘Symmetry operations: E, 8Cs, 3C, BS,, 65 Hall planes ofsymmety and are missing, the point group is T (pure rotational group, very rare); Ifall dihedral planes are removed but 3 g,, remain, the point group is T, ( [Fe(py)eI?* )9) Point Groups of high symmetry + 0, (octahedral) TiF 2, cubane C,H, ag | : Symmetry elements: E, /, 4S, 4C3, 3S,, 3C,, 60, 3 Cp, 30, 64 ‘Symmetry operations: E, 7, 8S,, Cy, 6S,, 6C,, 6C;, 3 C2, 3p, 854 Pure rotational analogue is the point group O (no mirror planes and no S,; very rare) 14) Point Groups of high symmetry + ly (icosahedral) BH? Cop Sig, Cx . ‘Symmetry elements: E, /, 65 jo, 6Cs, 108,, 10C;, 18C,, 186 Pure rotation analogue is the point group I (no mirror planes and thus no S,,, very rare)12) Systematic Symmetry Classification of molecules ae eee i on ae — te, be ly 7 (see) + Comey ‘4 available? — available? aS 2, T —— 8 an an \- —s[eavatabie? Rotational or Dinedra groups “Ser2 2 Geometry of Crystals Crystal systems (7) Bravais lattices (14) Triclinic Monoclinic ight symmetry elements 1,2,3,4,6, 1,3 Tetragonal Trigonal Hexagonal Cubic Point groups (32) Screw axes lide planes Spee ous (230): PA, PL P2, P2,, ete 222, P22,, ete mn, 2m 222, mm2, mmm PaFi ee P3, P3, ete PB, FB, BE o a osunmeny Ue Sap ouas of seven erystal systems and Bra ‘Anal lengths and a Tatice symbol Canie Thiee equal axes at right angles s ? =b=ca= 90° Body-centered 1 Face-centered F ‘Tetagomal Three axes at right angles, two equals imple P o=b#ea =9" Body-centered 1 Onthorhombic ‘Three unequal axes at right angle Simple P axbxea= 90° Body-centered 1 Bas-centered e Face-centered F ‘Trigonal* Three equal axes, equally inclined. Simple R e=dsca=pay ZH Hexagonal Two equal coplanar axes at Simple p 120° third axis at right angles bx c.a= p=, y = 120° Monoclinic Thee unequal axes, one pair not Simple P at right anglesa #6 # c. Base-centered c oxy = Z6 Trctinic Thee unequal axes, unequally Simple P inclined and none at right angles at b toad pty EW * Also called hombokedral