Symmetry and Elements of Group Theory of the transition dipole moment is g x u x g = u (antisymmetric) and hence the transition is not allowed. For u <> u transitions, we have u x u x u = and the transitions are again forbidden. For u <> g ones, we get u x u x g (symmetric) and they are allowed. In this section, we have shown that, by determining the symmetry of the integrand, we can identify the non-zero integrals and, in turn, derive the various, selection rules in electronic spectroscopy. 64.3 Molecular term symbols In our treatment on the bonding in linear molecules, we called the molecular orbitals of these systems either o or 7 orbitals, We now know that and are actually irreducible representations of the Coy oF Dock groups. For nonlinear molecules, names such as o and x no longer apply. Instead, we should use the symbols of the irreducible representations of the symmetry group to which the molecule belongs. So for the Coy molecules such as HS and H20, the molecular orbitals are ay, a2, by, ot bz orbitals. (Again we note that we use lower case leters for individual orbitals and capital leters for the overall states. This is a convention we also use for atoms: we have s, p, d, ... atomic orbitals and S, P, D, ... atomic states.) If the molecular orbitals have the symmetries of the inreducible representations, so do the states, or the molecular term symbols, arising from the electronic configurations. This is the subject to be taken up in this section. When the electronic configuration has only filled orbitals, there is only one state: ‘Pz , where Py is the totally symmetric representation. If the configura- tion has only one open shell (having symmetry 7) with one electron, we again have only one state: 7}. When there are two open shells (having symmetries T; and J) each with one electron, the symmetry of the state is Tj x Ij = Ty and the overall states (including spin) are $y andy Let us now apply this method to a specific example. Consider the ethylene molecule with Dz, symmetry. As can be seen from the character table of the Dz, point group (Table 6.4.2), this group has eight symmetry species. Hence the molecular orbitals of ethylene must have the symmetry of one of these eight representations. In fact, the ground electronic configuration for ethylene is (Lag)? (1b yu)? (arg) (2b 14)” ba)? Bag)” (1 3g)” (13)? (29)? Table 6.4.2. Character table of point group Dyy Dy E C20) €26) C20) § 6G) G2) e62) 4g 2 obo ot oto ogotoao4 eythe Be lot b-bd bt Ry a Be Lonloo-lo Ll at TTR oe Ap tot bd tt By LoL b-bd td Be Lob bb ea re ee ee 189190 Fig. 6.4.2. Some molecular orbitals of ethylene (int group Day). All ae completely Glled except Ibay in the ground state Symmetry in Chemistry - $ P® Pe |. So the eight pairs of electrons of this molecule occupy delocalized molecular orbitals 1ag to 1b3g, while the first vacant orbital is 1b2,..Note that the names of these orbitals are simply the symmetry species of the Dy point group. In other words, molecular orbitals are labeled by the irreducible representations of the point group to which the molecule belongs. So for ethylene there are three filled orbitals with Ag symmetry; the one with the lowest energy is called lag, the next one is 2dg, ete. Similarly, there are two orbitals with Byy symmetry and they are called 1b,y and 2byy. All the molecular orbitals listed above, except the first two, are illustrated pictorially in Fig. 6.4.2. By checking the Dzy character table with reference to the chosen coordinate system shown in Fig, 6.4.2, it can be readily confirmed that these orbitals do have the labeled symmetry. In passing, itis noted that the two filled molecular orbitals of ethylene not displayed in Fig. 6.4.2, lag and 1bj,, are simply the sum and difference, respectively, of the two carbon 1s orbitals So for the ethylene molecule, with an electronic configuration having only filled orbitals, the ground state is simply 1A, where Ag is the totally symmetric, species of the D2, point group. For the ethylene cation, with configura tion ...(143,)!, the electronic state is 7B3y. For ethylene with the excited configuration .. (1b3,)!(1b2,)!, the electronic states are 'Byy and *Byy, as Bou X Bag = Bru If, in the configuration, there are a number of completely filled orbitals and ‘one open (degenerate) shell with two (equivalent) electrons, there will be singlet as well as triplet states. To determine the spatial symmetry of these states, we make use of the formulas n=2: x (R,singlet) = ‘el x7(R) + xR?) 64.1, 2 (R, triplet) = '2lx7(R) — (R?Y] 64.12) In eqs. (6.4.11) and (6.4.12), x7(R) is the square of x(R), while x(R?) is the character of operation R?, which, according to group theory, must also be an operation of the group.Symmetry and Elements of Group Theory 191 46.4.3. Derivation ofthe electronic sates wrsing from configuration (@? of amolecule with Cy symmetry Cw FE 2C; dey A toon Az tor =n E 2-1 0 R ECs oy R EC; E X(R) in E representation 2-1 0 22(R) in E representation 4 100 X(R?) in E representation 2-1 2 x(R single) = "rpy2(R) + x0R}] 30 STE A(R. iple)= "202 (R) = xR) By For a molecule with Csy symmetry, when there are two electrons in an ¢ orbital; ic., when we have a configuration of (e)? (note that it takes four electrons to completely fill the doubly degenerate e orbital), we can use eqs (6.4.11) and (6.4.12) to derive the electronic states of this configuration, as shown in Table 6.4.3 According to Hund’s rule, among the three electronic states derived, *Ay should have the lowest energy. So for a molecule with C3y symmetry, contig- uations involving ¢ orbitals will lead to the following electronic states: (e)!, 2B; (e)*, 3g (lowest energy), '£, 11; (e)?, 2B; (e)4, 1Ay. Note that (e)! and. (6)3, being conjugate configurations, have the same state(s), analogous to the p! and p® configurations for atomic systems. Now let us turn to a three-dimensional irreducible representation for the first time, Take the Tog representation of a molecule with Oy symmetry as an example. For configurations (fz)! and (t2¢)°, the only electronic state is *Tp. (Note that azz orbital can accommodate up to six electrons.) For configurations, (tag)? and (f74)*, the states are #7}, (lowest energy), 'Tag, 1Ep, and "Aig. The detailed derivation of these states is summarized in Table 6.4.4. For (t2,)°, a closed-shell configuration, the only term is 'Ajg, a singlet state with totally symmetric spatial wavefunction. For the only remaining configuration, (2.)°, there will be doublet and quartet states. To derive these states, we require the following formulas: 1 ZC R ~ RY), (64.13) n=3: x(R, doublet) = 1 XR, quartet) = (3) (9B) — 3x RD (R?) + 2x (R?)] (6.4.14) In eqs. (6.4.13) and (6.4.14), x (R4) is the character of operation R? which of course is also one of the operations in the group. Applying these equations, wwe can derive the following states for the (Ing)? configuration: #42, (lowest energy), 771g, "Tog, and 7Eg, as shown in Table 6.4.4.192 Symmetry in Chemistry Table 6.4.4, Derivation ofthe electronic states arising from the configuration (1g)* and (tg? ‘of «coordination complex with Op symmetry oO E 8Cs 60: 63; 88. 30, 6a Ae to. ot ro1roaid ae tot st ororat z 2-1 0 0-1 20 Te 5 0 = too At Ts 5 0 1 “oo 1 1 An toro sto-t = = Ane tot batt B 2-1 0 o 1 2 0 Te 3 0-1 too tot nh at too 1 at R Fa G Se Son 0 R BG F coc FF ® BOER GC Sif on oe xRinTy 3 0 t “too 1 WR)inTe 30S “10 303 WR InTe FST 3 td xRsinge) 6 0 2 0 2 6 0 0 2 xp) § 0 “tt 3 1 oo = xRdowbe) § 1 0 0 0 & O -1 0 xReque) FL at =f ob dt -l ot 4 For the sake of completeness, we give below the formulas for open-shell systems with four or five equivalent electrons 1) 4 o 2¢R? X(R, singlet) = (5) Ux" (RY = 4x RXR?) + 3x7(R)], (6.4.15) 1 X(R, tiplet) = 3) (x4) — 2x7(R)x (RP) +2 (RY) — 2(RY), (64.16) Ble ) ("RD — 67 (R) x (RP) + 8x (RD (R?) = 6x (RS) + 3,7(R)] (64.17) n=5: x(R, doublet) = X(R, quintet) = ( ) (x9 RY — 23 CR) x (R?) — 47(R) x (R?) Ble + 6 (R)x (RA) + 3x (RY x7 (RP) = 4x(R) xR YI], (6.4.18) 1 a a X(R, quartet) = (=) UP RY = 5° RY CR?) + 57(R) x (REY + SR) CR) = 6x(R)], (6.4.19)Symmetry and Elements of Group Theory Table 6.4.5. The direct product of [1x II or a molecule with Cooy symmetry Coov E 2% cory at 1 1 = 14 -1 1 2 2e0se ° A 2 20529 o ° 2 20836 0 TUT 4 cosy + 200826 ° 1 A(R, sextet) = (& ) DP (RY — 10,3 R)x CR?) + 20x7(R) xR) = 30x (RY x (R4) + 15.R) x7 (R?) = 20x (R?)x(R*) + 24x (R9)] (6.4.20) Equations (6.4.15) to (6.4.20) may be of use for systems with J, symmetry. For such systems, we may be dealing with orbitals with G or H’ symmetry, which have four- and five-fold degeneracy, respectively. To conclude this section, we discuss an example involving a linear molecule, for which eq. (6.4.3) is not applicable. Consider configuration (17)! (2r)! for linear molecule XYZ with Cooy symmetry. As shown in Table 6.4.5, we can decompose the direct product II x IT into the symmetry species of the Cooy group, without using eq. (6.4.3) explicitly. To decompose /"(Il x Il), by inspecting x (C%), we can see that (I x 1) must contain A once. Elimination of A from /*(I1 x Il) yields characters (2, 2, ..., 0), which is simply the sum of E* and E-. Hence, after considering the spin part, it can be readily seen that the states arising from configuration Cn)! @rry! are 9A, 1A, 8E+, 1D, PE, and 1EW. In addition to the derivation of selection rules in electronic spectroscopy and electronic states from a given configuration, there are many other fruitful applications of group theory to chemical problems, some of which will be discussed in the next chapter. References 1. 1, Hargitai and M. Hargis, Symmetry through the Eyes of a Chemist, 2nd ed Plenum Press, New York, 1995 2. A. Vincent, Molecular Symmetry and Group Theory, 2nd edn, Wiley, Chichester, 2001 3. RL. Carter, Molecular Symmetry and Group Theory, Wiley, New York, 1998. 4. ¥. Ohm, Elements of Molecular Symmetry, Wiley, New York, 2000 5. FA. Cotton, Chemical Applications of Group Theory, 31d edn., Wiley, New York, 1990. 6. G Davison, Group Theory for Chemists, Macmillan, London, 1991 7. A.M, Lesk, Introduction Symmetry and Group Theory for Chemists, Kluwer, Dordrecht, 2004 193