‘The Franck-Condon Principle The equibrium positions of nuclei in a molecule result from their attractive coulombic interactions with all the present electrons and repulsive intecactions with remaining nuclei. Thus, the clon a peer ee aseet oce to rnc Fe crore eiye eae arnebell ae oe ees segue otltee ution cn Science stew ating molecules That why ete Scr shri ine eng seed faa ‘ion spectrum consists of many superimposed bands, These bands mer ge together to give single broad band with unresolved Sibras Matte aca for. i Fete rt of aband. ! i : i Se Another wo tates LM Word acy lace faster than geet Cansition uclecan, as Wavelength 2 —= el Sie soon ba. ground vibrational state to the v shown in Fig. 26. (Cuming pot ‘pases Molecular potenti energy —e Fig. 26. Franck-Condon n-ne. ‘Transitions to other vibrational levels also occur, but with lower intensity. In a condensed medium, the individual transitions are so broad that they merge together to give a broad band of absorption. 9.1 Classifications ot Electronic Transitions Electronic transitions in molecules can be broadly classified into ( 6-90" Transition : As o electrons are held more firmly in the mole-Fig 27-ElectoncTransions and relative energies of molecular orbitals ‘sitions of bands for different electronic transitions are st n are summarized Position of band and Remarks (Requires high energy which, . omophores which contain both x and 1 7 ions. For example, Carbon: non’ andn ally acolour enhancing gr chromophore by the sharing of the non-bonding, 1 absorption band towards the longer wavelength (the red ‘Auxochrome by itself does not act as chromophore. Some co ups are - OH, ~ OR, ~NH,,~ SH, etc ‘and Intensity Shifts hromic shift (or Effect). It leads to the shift of absorption maximum wavelength. Itis also known as Blue shift and is due to either the re jugation or change in polarity ofthe solvent. For exaziple, absorp- tion maximum of aniline shifts from 280 mp. to 200 my in acidic solutions, which ° results in the formation of CJHNH, from CjH.NH.. sly, the lone pair is resent on ~ NH, group and hence conjuge‘ion is removed which results absorption maximum. ‘hrome. It is also known as rent. For example, the n>" jochromic shift when the polar- (b) Bathochromic shift (or effect) It ead: longer wavelength due to the presen: 0 result by the change Wavelength Fig. 28, Te various shifts enas ad Dae 18.4 The Contribution of Electronic Transitions to the Colour of Objects Many of the colours ofthe objects in the world around us arise from transitions in which electrons are shifted from one orbital of a molecule orion into another. As [| " <_o, |Fig. 28. Anarst' colour wheel Green colour of vegetation. meer erate een! fore Kind Me chromophore activity is due long confonant sl taditionncdeon og 6 ees Present i ‘eating eet Gr a n° transition of cyano group also appear at &< 220 nm but its €< 100). system, the amines, ethers, alcohols and thiols show this type of ~ "transition. (0 Two bands of medium intensity (€=1000 to 10,000) both with 2am > 200: are shown by simple aromatic system. In non-polar solvents, the Jonger wavelength band shows a great del of fine structure. Ifthe substituent on the aromatic ring increases the length of the conjugated system, it will increase the ‘molar absorptivity above 10,000 A third band near 200 nm is displayed by poly ‘lear aromatic systems. They also show fine structure. -y -M group para to Jet no bonding pat donation (by the +M group) selective, eaeg enenian tothe elon withdrawing ~M group the shift a is rene rae vidual shit (eg, p-itroanilne and p-nitrophenol.) change, '§ Pair ‘availability’is changed, the position of ayy Will also 4(—M) group ortho or meta to a from that ofthe isolated chromophores”) BTOUP Produces merely a small shill SOLVED EXAMPLES highest occupied molecular oF: lecular orbital, LUMO, (3). The 0.2 Identify the geometric isomer of stilbene from thee rales of 294 and zn. H 4 H os dened poney CHs CH CH oH rrmvsebone ‘Ans. The extent of conjugation in trans-silbene is more in comparison to that in cis-isomer. This is because, the steric strain in the cirisomer, prevents complete oplanarity necessary for full conjugation. As a consequence, the cis-stilbene is ‘expected to absorb at shorter wavelength. Hence, rane sulbene Diam [tomer ‘aeatibene Dont hn Q. 3. Suggest a reason for the indicated differences between the absorption ‘maximum of ortho-and para-methyl acetophenone. 1 0 oO oO 1 a wQia — Qhe cH — tie | ‘Ans. The methyl group in the ortho-methyl acetophenone (II) twists the carbonyl group out of conjugation with the aromatic ring. However, in the paré- isomer (I; carbonyl group is in conjugation with aromatic ring s0 its absorption ‘maxima (pa) is also higher. Q.4. Explain for aniline, the following trends i yy? Neateal ‘Acidic 203 nm Medium con 230nm [_ So. a |jdrogen to gin wer allthe three (X. Yand eae Vas are unsaturated open cain hydrocarbons rebate and one triple bond : aoe tate with ammmonical AgNO, Sothe rg (since and Zgivea white precipi send i present atthe en ofthe chain in each compound Moreover, X doesnot give a white precipitate with ammonical AgNO, Be the end ofthe chain. {Since both X and ¥ exhibit an absorption maximum (pu) at -230 mm while Z shows itatless than 200 nm. Hence both X and Y have conjugated bonds triple bond in ts does not c-C=C-Cae forY But the Z has non-conjugated bonds. C=C-Cac-¢ for X €=C-C-C=ChorZ Thus, X is 4-penten~ Xis4-penten-2-yne (CH, =CH-C=C-CH,) Se tsa Te Yis 3-penten~ ‘penten=1=yne - (CH; CH=CH - C= CH). Eanes ere Zis4-penten ~ 1- ‘penten-1-yne (CH, =CH - CH, - CsCH) Sy ames arr i 16 Of Ay fF X indicates that it isa conjugated cyelohexadiene Xand Y are and (1deycaheradiene) (Aeyeatensiene) Example 7. A diene has Rng at 175 nm. What do you know from this data ? Solution. As the value of Aja, (175 nm) lies in the far UV region hence the two in the diene are isolated double bond. (CaF) has i intense peak at 217 nm in its UV spectrum. peak at 217 nm suggests that the diene is a conjugated ‘Example 9, Discuss some qualitative application of electronic (UV-cisble spectros: copy). Solution. Qualitative applications of electronic (UV-visible) spectroscopy + fan be used to measure the extent of multiple bond or aromatic jugation within molecules (@ Itcanbe used to differentiate (@) Conjugated dienes from nonconjugated dienes, “onjugated dienes from conjugated trienes ‘aB- unsaturated ketones from their By-analogs, ete fined molecules as the degree of ‘-orbial overlap in 2-substit Zpectrum can be easly correlated with angular distortion. Trean alno reveal the number and location of substituent attached fo the carbons of the conjugated system. {o) Teean als predict the presence of an aromatic ing itself: lLin some o sunmaczed A TEXT lect _aitatve espe of ee in FB 3 below in OF ENGINEERING Oe, onic absorption spectroscopy & SPECTROSCOPY is tadiene requires less energy for the n—> x" ym tals. One ground state x bonding orbital ited state x” antibonding orbital. The energy difference between them KCal/mole. yene has two bonding (x, and m,) and two antibonding (x3 and x;) and m) are respectively, more stable (m;) and x.) than x bonding 1} and xj) are respect ing orbit Energy absorption, ore stable (ns) and less stable (n) than. shown in Fig. 27 refer page 156). absorption band, can thus occur st occupied molecular orbital () CH, = CH- CH, -CH=CH-CH, acd ey aan 1 4-Hexadiene ° r (iif) (@) CH, = CH- CH, - C- CH, ~ CH, ~CH, Tee gest seen aan “Pheptl-enone ° 1 () CH,— CH =CH-C-CH,-CH, -CH, TORIES SS RSC RET “hept enone ° ° . Fl (i) cH, -C-{) and (t) Orvorn-€-cx Ethyl phenylketone enay methyl ketone (propephenone) (Phenyl acetone ei 8 HH ©) @ 11K Hand © CE a 3 ‘ 2 34 A WH 1,2ihydronapthalene 1, 4-dinydronaphitalene