settstudy exercises te down the spin selection rule, 1. Lans, See text} ‘What is the d configuration and the spin multiplicity o ground state of (@) a TH" and () a V2" font SY oF the Vans. (a) d'; doublet; (6) a5 triplet} 4, Why isa transition from a 1, to an e, wee orbital spin allowed in Ans. Triplet to triplet; see question 1} ——_—_—_—_____ Electronic spectra of octahedral and tetrahedral complexes Electronic spectroscopy is a complicated topic and we shall restrict our discussion to high-spin complexes. This corre- sponds to the weak field limit. We begin with the electronic spectrum of an octahedral d' ion, exemplified by {TWOH;},P*. The spectrum of (Ti(OHL)«|"* (Figure 21.4) exhibits one broad band. However, close inspection shows the presence of a shoulder indicating that the absorption is actually two closely spaced bands (see below), The term symbol for the ground state of Ti (d', one electron with L=2,S=})is*D. In an octahedral field, this is split into "Ty and 7E, terms separated by an energy Acc.. More genet- ally,itcan be shown from group theory that, in an octahedral or tetrahedral field, D, F, G, H and 1, but not S and P, terms split, (Lanthanoid metal ions provide examples of ground state Hand I terms: see Table 25.3.) “Tem Components in an octahedral el s A 4 P Te i 7 on ‘ F Aug + Tag + Tie 4 ¢ Aig + By + Tag + Tre H Ey + Tig + Te + The 4 : 5 Aug + Ag + Eg + Tig + T+ Toe Similar splittings occur in a tetrahedral field, but the g | ‘re no longer applicable. The splittings arise because the S, P, D, F, G, H and I terms "tro degenerate torial na cetera Sl this splits into the f- and e, sets of orbitals (Figure 21.2). For the dion, there are therefore two possible coniawrston tade@ or tneteg!, and these give rise to the "Tae (horn Sate) and 2, (excited state) terms. The energy ssPOraties between these states increases with inoreasing fle SATE Figure 21.18). The electronic spectrum of Ti cere @ transition from the Tay to the E, level: the e Chapter 21 « Electronic spectra 663 Increasing Age Fig. 21.18 Energy level diagram for a d' ion in an octahedral field. transition depends on the field strength of the ligands in the octahedral Ti(II1) complex. The observation that the electronic spectrum of [Ti(OHs)<)"* (Figure 21.4) consists of two bands, rather than one, can be rationalized in terms of a Jahn-Teller effect in the excited state, ty°e,!. Single jccupancy of the ¢, level results in @ lowering of the degen- eracy, although the resultant energy separation between the ‘wo orbitals is small. A corresponding effect in the fag set is even smaller and can be ignored. Hence, two transitions from ground to excited state are possible. These are close in energy and the spectrum exhibits two absorptions which are of similar wavelength For the d” configuration (e.g. Cu’*) in an octahedral field (actually, a rare occurrence because of Jahn-Teller effects which lower the symmetry), the ground state of the free ion (°D) is again split into 77, and *£, terms, but, in contrast to the d' ion (Figure 21.18), the *E, term is lower than the *7zy term. The d? and d' configurations are related by a positive hole concept: d° is derived from a d'° configuration by replacing one electron by a positive hole; thus, whereas the d' configuration contains one electron, 4° contains one *hole’ (see Section 21.6). For a d? ion in ‘an octahedral field, the spitting diagram is an inversion of that for the octahedral d' ion. This relationship is shown in Figure 21.19 (an Orgel diagram) where the right-hand side deseribes the octahedral d' case and the left-hand side describes the octahedral d” ion. Just as there is a relationship between the d' and d° configurations, there is a similar relationship between the d* and d® configurations. Further, we can relate the four configurations in an octahedral field as follows. In the wweak-field limit, a d° ion is high-spin and spherically symmetric, and in this latter regard, d°, d° and d'® config- trations are analogous. Addition of one electron to the high-spin d° ion to give a d® configuration mimics going, from a d° to d' configuration. Likewise, going from d° to 5nn Oe ean i Fore !, d® octahedral dtd? tetrahedral 2d weabetal d',d? octahedral a Fig. 21.19 Orgel diagram for d', d* (high-spin), d® (high- a) ‘and d° ions in octahedral (for which Tz, and E, labels wre ejevant) and teuahedral (E and Ts label) fel. In contrast to Figure 21.18, multiplicities are not stated because they depend on the d” configuration. d* by adding a positive hole mimics going from d'° to d°. The result is that the Orgel diagrams for octahedral d' and d® ions are the same, as are the diagrams for octahedral dé and d° (Figure 21.19). Figure 21.19 also shows that the diagram for a d' or d° ion is inverted by going from an octahedral to tetrahedral field, Because the Orgel diagram uses a single representation for octahedral and tetrahedral fields, itis not possible to indicate that Av = $Aoq. Tetrahedral d* and d° ions can also be represented on the same Orgel diagram. Finally, Figure 21.19 shows that for each of the octahedral and tetrahedral d', d*, d® and d” ions, only one electronic transition (see Box 21.2) from a ground to excited state is possible: * for octahedral d! and d®, the transition is Ey — Tay * for octahedral d* and d°, the transition is Ta, — E, Table 21.9 A shorthand table of microstates for a d? considered, and each electron has m, = i + and *P terms. Table 21.7 provides the conden’ omplete table of Imicrostates are grouped so | and d”, the transition is 7, tetrabedrl a and d°, the transition is i ve ae -_ gpinvallowed (n0 change in totay in is spin-al e if fucronic spectrum of each ion exe For sake of completeness, the notation fing vin above should include spin muting joctahedral d', the notation is 2p} high-spin, octahedral d* it is *To, - ‘z, fe _ ealogous manner to grouping d’, ang a oa sider together d?, d°, d” and q¥ jg é for for tetral Each trans! and the ¢ absorption. transitions Biv 28 +1, €.B. fOr can C00 tot al and tetrahedral fields. In order to disgye'® oxtaea spectra. of these fons, the terms that ari ‘< e tion must be known, In an absorptioy, ‘erned with electronic transitions f, or more excited states, the d° configurat trum, we are conc . to one Tansitions ground state r sible from one excited state to another, but thr pap Pmt is 20 1ow that they can be ignored. Two poi particularly important: selection rules restrict electronic transitions 10 thy between terms with the same multiplicity; the ground state will be a term with the highest pia mij, plicity (Hund’s rules, see Seetion 21.6). Om thy . In order to work out the terms for the & configuratoe,, table of microstates (Table 21.7) must be construcie, However, for interpreting electronic spectra, we ni concern ourselves only with the terms of maximum gia multiplicity. This corresponds to a weak field limit. For te d? ion, we therefore focus on the 3F and >P (triplet) tems. These are summarized in Table 21.9, with the correspontag microstates represented only in terms of electrons with» ~ +} It follows from the rules given in Seetion 21.6 tht the °F term is expected to be lower in energy than te ae a octahedral field, the *P term oes not sh aise cs ae, The *F term splits into *7i., % aan a 's. The “Ti¢(F) term corresponds to a ly ine and is triply degenerate because there # Ways of placing two electrons (with parallel si cont ‘ ates erttion; only a high-spin case (weak field limit) is Sto show the derivation of the °F microstates for a d? ioTor, Ty ot, Aagot dy 7 ° 2,47 tetrahedral ae “ pera 2d? ccahotat 2,4 waked Fig. 21.20 Orgel diagram for a? ford, @?, d? sp) in oetahedal or which Feats a ions (high ses) and waked Ce ecient eek Molipisities are not stated because tity depend ot Siren mp aeate tng labels are appropriate Tips Ta ad in any two of the dey, dye and dy, orbitals. The *Azy te corresponds to faye," arrangement (singly de ak The °Toz and *Tig(P) terms equate vith nce configuration; the lower energy *Tz, term arises from placing two electrons in orbitals lying in mutually perpendi- gular planes, e.g. (dy)'(da)', while the higher energy Tg(P) term arises from placing two eleetrons in orbit ying in the same plane ¢.g. (dey)! (de 2)'- The energies of the Tig(F), °Tags "Ang ad *Tig(P) terms we shown on the right-hand side of Figure 21.20; note the effet of neve field strength. Starting from this diagram and using ihe 78 arguments as forthe dd", d° and d” fons we can derive the ‘complete Orgel diagram shown, re 21.20. At increased field strengths, the lines describing the T,(F) and Tig(P) terms (or T;, depending on whether we 3° dealing with octa- hedral or tetrahedral cases) curve WA from one another: ae erection between term of the 5 symmets roel hey are not allowed to cross (Me nnon-crossing rule). aoe eygure 21.20, we can see Why Th Pere observed in the electronic spectra a? d°,d” and dont hedral and tetrahedral complesst: The transitions sted sates, and are allowed, €8. the ground to excuse ved transitions are “Tag for an octahedral d° ions the allowed 21.21 illus- for an cee Ang and ‘TislP) dag, Figure 21-21" age Tal) A a ick) eo trates spectra for octhedeet Ay, lt ramsiions n-spin d i ee “Folens a : s fare pat be sions are ‘extremely weak. electrons). Associated absorpti ‘ooo 15000 20000 2500 $000) wen Fig. 21.21 Electronic spectra of | f(OH2)6P* (0.101 moldm) and into (O315moldm-” in corejts NH, solution) showing three absorption Danes BUEN ar absorptivity, ¢, ae Zlated to absorbance Po ike Beer-Lambert law (equation 21,12). (This Gauss ® by the Bectata provided by Christian Reber, see: M- Tries tase chose Hl Belisle and C. Reber (2000) J. Chem, Ede oer G70; hp: /ichemed. chem. ise.edu/JCEWWW/ ‘Artiles/JCENi/JCENi.html] ‘The electronic spectrum of am aqueous solution of ( (en) exhibits broad absorptions with Agax ~ 325, 550 and 900.nm, (a) Suggest assignments for the electronic transitions. (b) ‘Which bands are in the visible region? (@) [Ni(en)sP* is « Nid, a complex. From the Orgel diagram in Figute 21.20 the three transitions can be assigned; fonest wavelength corresponds to highest energy transition: 900 nm assigned to ?Tag — "Ane 550m assigned 10 °7),(F) — Sze 325nm assigned to *T\p(P) — * Arg (b) Visible region spans ~400-750 nm, ‘am, 80 ra Qo isin ivrange Ge 202) Self-study exercises 1 onthe —— [Ni(en)3|?*, which is closest to the ‘of the spectrum? ans. Look at Appendix 4] 2. Does ame 3 Tag — "Ang indicate an absorption or an ‘emission band? ans. Look at Box 21.2) 3. Why are the three transitions for wi i Why ate es transi for (Ni(en)s|** (a) spin-allowed, eae eee eee eee