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1 Spectroscopy in Inorganic Chemistry

2 2 Diatomic molecule C v and D h HCN H-H

3 3 contribution orbital electron Σ 0 σ 1 Π 1 π 1 Δ 2 δ 1 Φ 3 δ 1 Σ + Σ -

4 4 Linear molecule NO 2s+1 2 Π A 1 =Σ + 0 A 2 =Σ - 0 E 1 =Π 1 E 2 =Δ 2 E 3 =Φ 3

5 5 linear, E 2C... &sigma v rotations quadratic A 1 =Σ z x 2 +y 2, z 2 A 2 =Σ R z E 1 =Π 2 2cos(Φ)... 0 (x, y) (R x, R y ) E 2 =Δ 2 2cos(2φ)... 0 Character table for C v point group E 3 =Φ 2 2cos(3φ) (xz, yz) (x 2 -y 2, xy)

6 6 Character table for D h point group E 2C... σ v i 2S... C' 2 linear functions quadratic, rotations A 1g =Σ + g x 2 +y 2, z 2 A 2g =Σ - g R z E 1g =Π g 2 2cos(φ) cos(φ)... 0 (R x, R y ) (xz, yz) E 2g =Δ g 2 2cos(2φ) cos(2φ)... 0 E 3g =Φ g 2 2cos(3φ) cos(3φ) A 1u =Σ + u z A 2u =Σ - u E 1u =Π u 2 2cos(φ) cos(φ)... 0 (x, y) E 2u =Δ u 2 2cos(2φ) cos(2φ)... 0 E 3u =Φ u 2 2cos(3φ) cos(3φ) (x 2 -y 2, xy)

7 7 Tetraphenylcyclopentadienone σ* π* n b n a π σ ground state excited state excited state

8 8 energy

9 9 Spin-Orbit coupling J s 2 S L l 1 s 1 l 2

10 10 Configuration interaction E e g?? t 2g E>E' E'

11 11 Excited states configurations Ground state Singly excited conf. Doubly excited conf.

12 12 H 1s H H H H H 1s 2 N 2 ( A B ); 2 1 N 21 ( A B ); ); antibonding MO antibonding MO MO

13 13 ' B 1b ' B 1a Configuration interaction Initial state Final state C.I. ' ΨB 1b ΨB 1a ' ' B 1b B 1a ' C.I. ' ΨB 1b ΨB 1a '

14 14

15 15 Initial state energy E 0 1 E H 12 E E H 12 Initial state energy electron-electron repulsions

16 16 E 1 = ½[E E ((E 10 ) 2 + (E 20 ) 2-2E 0 1 E H 122 ) ½ E 2 = ½[E E ((E 10 ) 2 + (E 20 ) 2-2E 0 1 E H 122 ) ½ Initial state ' B 1b ' B 1a Final state C.I. ' ΨB 1b ΨB 1a '

17 17

18 18

19 19 Criteria to aid in band assignment n π* - molar absorptivity < Blue shift in high dielectric or hydrogen-bonding solvents

20 Dielectric Constant Pentane 1.84 Hexane 1.88 (25 C) Pyridine 12.4 Heptane 1.92 Methyl Isobutyl Ketone (25 C) Iso-Octane 1.94 Methyl n-propyl Ketone Cyclopentane 1.97 Isobutyl Alcohol Methoxyethanol Cyclohexane ,2,4-Trichlorobenzene 2.24 (25 C) n-butyl Alcohol (25 C) 1,4-Dioxane 2.25 Methyl Ethyl Ketone Toluene 2.38 (25 C) Isopropyl Alcohol (25 C) n-propyl Alcohol (25 C) 1,1,2-Trichlorotrifluoroethane 2.41 (25 C) Acetone 20.7 (25 C) Triethylamine 2.42 (25 C) o-xylene 2.57 Ethyl Alcohol (25 C) Ethyl Ether 4.33 N-Methylpyrrolidone 32.2 (25 C) Chloroform 4.81 Methanol (25 C) N,N-Dimethylformamide (25 C) n-butyl Acetate 5.01 Acetonitrile 37.5 Chlorobenzene 5.62 (25 C) Ethyl Acetate 6.02 (25 C) Dimethyl Acetamide (25 C) Glyme 7.20 (25 C) Dimethyl Sulfoxide n-butyl Chloride 7.39 Propylene Carbonate 64.9 Water 80.1 Tetrahydrofuran 7.58 (25 C) Trifluoroacetic Acid 8.55 Dichloromethane 8.93 (25 C) o-dichlorobenzene 9.93 (25 C) Ethylene Dichloride (25 C) 20

21 21 e g Blue shift e g e g

22 22 e g With increasing polarity n π* transitions are shifted to lower wavelengths (blue shift). This shift is due to unpaired electrons (orbital energy decreases n) n π* Increase solvent polarity

23 23

24 24 Formic acid H-C(=O)OH 101 C g/ml 1.41 D n-butanol CH 3 -CH 2 -CH 2 -CH 2 -OH 118 C g/ml 1.63 D Isopropanol CH 3 -CH(-OH)-CH 3 82 C g/ml 1.66 D n-propanol CH 3 -CH 2 -CH 2 -OH 97 C g/ml 1.68 D Ethanol CH 3 -CH 2 -OH 79 C g/ml 1.69 D Methanol CH 3 -OH 65 C g/ml 1.70 D Acetic acid CH 3 -C(=O)OH 118 C g/ml 1.74 D Nitromethane CH 3 -NO C g/ml 3.56 D Water H-O-H 100 C g/ml 1.85 D

25 25 Hydrogen bonding solvents e g π* n n π* π* n

26 26 Solvent M. Homocianu et al. / Journal of Advanced Research in Physics 2(1), (2011)

27 27 Acidic media

28 28 Electron-donating group chromophore < < < Electron-donating group

29

30 30

31 31

32 32 π π* his transition is available in compounds with unsaturated centres, e.g., simple alkenes, aromatics, carbonyl compounds, etc. this transition requires lesser energy then transition in a simple alkene, although several transitions are available, the lowest energy transition is the π π* transition and a absorption band around nm in unconjugated alkenes is due to this transition in the case of, e.g., saturated ketones, the most intense band around 150 nm is due to π π* transition

33 33 Red shift e g

34 34 Solvent effect (polarity) π π* e e g Increase solvent polarity g

35 35 K- Band One may designate the UV absorption bands by using electronic transitions or the letter designation. The band due to π π* transitions in a compound with conjugated π system is usually intense (ε max.>10000) and is frequently referred to as the k-band (germankonjugierte). The examples of the compounds in which k-band appears are butadiene, Mesityl oxide. Benzene itself displays three absorption bands at 184,204 and 256nm and of these the band at 204nm is often designated as k-band, and this used in other benzenes as well. Eg. Conjugated diene, triene, polyene, enones and aromatic rings

36 36 R- Band The n π * transition (R-band german radikalartig) in compounds with single chromatographic groups i.e., carbonyl or nitro are forbidden with ε value less than 100. In conjugated systems the energy separation between the ground and excited states is reduced and the system then absorbs at longer wavelengths and with a greatly increased intensity (k-band is intense and at longer wavelength). Moreover, due to the lessening of the energy gap, the n π * transition due to the presence of the heteroatom and lone pair i.e. the r-band also undergoes a red shift with little change in intensity. Eg. Acetone, acroline, methyl vinyl ketone, acet aldehyde, acetophenone, croton aldehyde

37 37 B-Band These bands are observed in aromatic compounds and hetero aromatic compounds. Here B refers to Benzenoid bands Eg. Benzene, tolune, acetophenone, benzoic acid, napthelene, styrene E- Bands Such band originate due to electronic transition in the benzenoid system of the ethylinic part enclosed in cyclic conjugation. Here E refers to Ethylinic. These are further classified as E1 and E2 Eg. Benzene, nepthelene, anthracene, quinolene

38 38 The intensity electronic transition Oscillator strengths

39 39

40 Transition moment integral Ground state electronic wave function Excited state electronic wave function 40 +x ƒ = Ψ e MΨ e dv =D -x ^ Electric dipole moment operator ex 2

41 41 moment integral

42 42 Electric dipole moment M=Σer M = e 1 r 1 + e 2 r 2 + e 3 r 3 +

43 43 moment integral Then Ψ g ΣerΨ g dτ ^ Ψ g MΨ g dτ Ψ g ΣerΨ ex dτ M=Σer

44 44 Transition moment integral ƒ = Ψ e MΨ e dv =D -x +x ^ ex 2

45 45 ^ Ψ e M x Ψ e dv ^ Ψ e M y Ψ e dv ^ Ψ e M z Ψ e dv

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