Krenvouge Let vey, UlE/ ranean PEctocestepy ‘Spectroscopy may be defined as the study of interaction“Between electromagnetic radiations and matter. Spectroscopy has a wide range of applications. It is heavily used in astronomy and remote sensing. Most large telescopes have spectrographs which are used either ‘to ‘measure the chemical composition and physical properties of astronomical objects or to measure their velocities (from the doppler shift of the spectral lines). In medical diagnosis, various techniques employed (such as MRI, EEG, X-iay etc.) are based on spectroscopy. It has a wide range of applications in the study of atomic and molecular structure. It is an important tool in the hands of analytical chemists for the identification and quantitative analysis of chemical substances. As we shall be concemed with what spectroscopy can tell us of the structure of matter, so it is essential to discuss briefly the nature of electromagnetic radiation and the sort of interactions which may occur. Electromagnetic Radiation Aecotromagnetic radiation is a transverse energy Schematic of an electromagnetic wave wave that is composed of an osciliating electric 19868.M. Tissue field component, £, and an oscillating magnetic ‘won eke com field component, M. The electric and magnetic E fields are orthogonal to each other, and they are orthogonal to the direction of propogation of the v wave. A wave is described by the wavelength, 2, which is the physical length of one complete M propagation oscillation, and the frequency, v, which is the direction number of oscillations per second. The figure shows one wavelength of a wave of light Electromagnetic radiation, of which visible light forms an obvious but very small patt, may be considered as a simple harmonic wave, propagating from a source and traveling jected). This can be represented by the sine wave equation y = A sin 2nx/A, where i is wavelength of the wave. Energy associated with wave is given by the relation E = hv where v is the frequency (units: sor hertz) of the waye and is given by_v = c/A; h is Planck’s constant (h = 6,63 x 10% 8). Since A= vive vwhere vis the wave number (units: om"), The names we give electromagnetic radiation for different wavelength and frequency ranges are listed in the order of their energies and collectively called electromagnetic ‘spectrum, Electromagnetic Spectrum Electromagnetic spectrum constitutes all possible electromagnetic radiations arranged according to the order of their increasing (or decreasing) energies. As already mentioned : oFelectromagnetic radiation at a particular wavelength 2 has an associated frequency v and energy E. Thus electromagnetic spectrum may be expressed equally well in terms of all the three quantities. In the increasing order of frequency (and hence energy) the regions of electromagnetic spectrum are as follows i 1. Radiofrequency region: Electromagnetic waves corresponding to frequencies 3 x 10° 3 x 10!° Hz or wave length 10 cm to 1 om lie in this region. This amount of | energy change arises from change in spin of electron or nucleus and is of the | order of 0.001 to 10 J/mol. 2. Microwave region: Electromagnetic waves corresponding to frequencies 3 x 10! — 3 x 10” Hz or wavelength 1 cm to 100 um lie in this region. Separations between rotational energy levels of molecules are of the order of hundreds of Joules per mo! and a transition of an electron from one rotational level to the other is accompanied by absorption of energy in this region. | Infrared region: Electromagnetic waves corresponding to frequencies 3 x 10"? 3 x 10* Hz or 100 jum to 1 jum lie in this region, These radiations. (of corresponding energy of the order 10* W/mol) are absorbed when transition takes place between | vibrational levels, The study of such absorptions is called vibrational spectroscopy. 4. Visible - UV regions. Radiations corresponding to energy changes of the order { hundreds of kilo joules (v = 3 x 10-3 x 10° Hz or = 1 um to 10 nm). | Absorptions in this region occur due to transition of valence electrons between electronic energy levels. So, study of these transitions is termed as electronic spectroscopy. Visible region lies between 400 nm to 800 nm whereas the rest is 4 UV region. 5. X~ ray region: Energy of these radiations fall between ten thousands of kI(v = 3 x 10'S —3 x 10'* Hz or A= 10 nm to 100 pm). These radiations are emitted or absorbed when inner electrons of an atom or a molecule change energy. 6. y-ray region: y radiations are associated with energy equal to 10° — 10! Jg-atom (v= 3x 10-3 x 10° Hzor A= 10 pm or less). Such a high energy change occurs due to rearrangement of nuclear particles, Cosmic rays possess energy even higher toy rays but are found only in outer space. | Type of Radiation | [samma-rays (nuclear [X-rays inner electron i outerdeeron ultraviolet = oe | [visible outer electron j —— | | molecular vibrations i icrowaves molecular rotations, electron spin flips* | |radio waves nuclear spin flips* Given below is a representation of entire electromagnetic spectrum. The visible light constitutes only a small portion of entire spectrum and is shown separately. The energy E of an electromagnetic radiation is. quantized. In 1900, Max Planck gave the idea of quantization of energy. That is, the energy of an oscillator is discontinuous and any change in its energy can occur only by means of a jump between two distinct energy states. The idea was later extended to many other forms of energy of matter. This Inplies that a Transition can take place between two distinct energy levels associated with an atom or molecule and energy equal to the difference between these two levels AE can only be absorbed or emitted. If we take a molecule or atom in state 1 associated with energy E) and direct on to it a beam of radiation of a single frequency v (monochromatic radiation), the energy will be absorbed from the beam of radiation and atom or molecule will jump from state 1 to state 2. A detector placed to collect the radiation after its interaction with the species will show that intensity of the radiation has decreased. If we use a beam containing a wide range of frequencies, the detector will show that energy has been absorbed only from the frequency v = AE/h, all other frequencies remain undiminished in intensity. AE is the difference in the energies of level 1 and level 2. In this way we have produced an absorption spectrum. Altematively, the species may already be in energy state 2 and may revert back to the state 1 with emission of radiation, The detector would show this tadiation to have frequency _v = AB/h. The emission spectrum so obtained is complementary to the absorption! Spectrum discussed above. Spectrum: The data obtained from spectroscopy is called a spectrum. A spectrum is a plot of intensity of energy detected versus wavelength (or frequency or wave number or ‘mass or momentum ete.) — 3spectrum can be used to obtain information about atomic and molecular energy levels, olecular geometries, chemical bonds, interactions of molecules, and related processes’ Often, spectra are used to identify the components of a sample (qualitative analysis). Spectra may also be used to measure the amount of material in a sample (quantitative analysis). Atomic spectroscopy deals with the interaction of electromagnetic radiations with atoms. As explained above, both absorption and emission atomic spectra can be observed for atoms. Thus, atomic spectroscopy can be categorized into two types — atomic absorption spectroscopy and atomic emission spectroscopy.fIn_atomic _abso1 Spectroscopy. the atoms are in their ground states initially and can be excited b iiradiating them with radiations of appropriate ven by difference of gl ind and excited energy levels/ These energy levels are occupied val orbitals and lowest unoccus oybitals Tespectively. The excitation o1 Valence electrons takes place during the transition, uring “alone Smtision g 1 the electrons are already in excited state and rever ‘ground state with emission Fradiation of frequency equivalent to the energy difference of their ground and excited. “energy tevels ee : An important application of atomic spectroscopy is, sorption and Flame emission spectroscopy. The flame is used to bring the sample solution to gaseous state in “tormer and excite the atoms to. higher state besides bringing the sample solution to gaseous state for later. These techniques are used for detection of trace elements. For example Flame absorption spectra are used to detect Mg in water, V in lubricating oils, Cd, Cu, Zn, Ni, As etc. in soil, Sn in canned fruit juices and flame emission spectra are obtained for analysis of alkali s in biological fluids or tis: Molecular spectroscopy deals with the interaction of electromagnetic radiations with molecules. As compared to atomic spectroscopy, it is relatively complex. Before discussing different types of molecular spectroscopy, let us discuse the kind of energies a ‘molecule possesses, rhe energy possessed by a polyatomic molecule may be due to contribution from sranslational energy (arising from change of its centre of gravity as a result of motion), Aeration: -farising from to and fro motion of the nuclei of the molecule so that iS centre of gravity does not change) and rotational energy (arising from its rotation about an axis perpendicular to the intemuclear axis and passing through the ecste of As an approximation, suggested by Max Born and J. Robert Oppenhiemer, nuclear motions can be separated from electronic one because the nuclei being massive fixing position of nuclei. Therefore change in translational energy can be ignored while calculating the total molecular energy. So, the total energy of a molecule is considered as 4the sum of electronic, viberational and rotational energies associated with corresponding electronic, viberational and rotational levels. E=E etectronic + E vitecational + E rotational Associated with each electronic ievel is a number of viberational level and with each viberational level a series of rotational levels are associated. The order of energies of these levels are E ctecronic > E vtertirat > E roaionat. All these energies are quantized. The order of magnitude of these energy changes are A E elecronic AE viterationst X 10? = DE rorsionat X 10° Electronic Spectroscopy Electronic spectroscopy deals with the excitation of valence electrons of the molecules or species fic ¢_lower electronic level to higher electronic level. The energy thus absorbed lies in the ultraviolet or visible region of the” electromagnetic spectrum. The UV region extends from 100-400 am whereas the visible region extends from 400-800 nm. Below 200 nm, O2 absorbs strongly. Therefore for all practical purposes, wavelength range of 200-800 mm is chosen Electronic transitions When an atom or molecule absorbs energy, electrons are promoted from their ground state to an excited state i.e. from the outermost filled orbital (HOMO) to lowest in ‘energy empty orbital (LUMO). ‘There are three types of electronic transitions which cen be considered; 1. Transitions involving x, o, and n electrons 2. Transitions involving charge-transfer electrons 3. Transitions involving d and felectrons Absorbing species containing x, c, and n electrons Absorption of ultraviolet and visible radiation in organic molecules occurs due to excitation of electrons from bonding or non bonding orbitals (ground state) to the antibonding molecular orbitals (excited state) which are usually vacant when the molecule is in ground state. The electrons present in x, 0, and n orbitals are called m, o, and n electrons. The antibonding orbital associated with o electrons is 6, with nis x* while n (non bonding) electrons are not associated with any antibonding molecular orbital since they are not involved in bond formation. Consequently, ’n electrons are present in the atomic orbitals which have higher energy as compared to 7m electrons.Possible electronic transitions are (i) 6 -> a" transitions (ii) n > 0° transitions (i n— 3 transitions (iv) x — 1° transitions | Antibonding o* ast ee . evap Antibonding 1 Lone \adlr Controls Non-bonding p 1) West Energy —> oh. Bonding 1 | contain ane | oo dng pai Le Bonding o . en | oo Transitions | An electron in a bonding orbital is excited to the corresponding antibonding orbital. ‘The energy required is large. These transitions are shown only by those compounds in Fwhich all the electrons are involved in the bond formation, e. 2g. saturated hydrocarbons. For example, methane (which has only C-H bonds, and can only undergo ‘6 ~>G" transitions) shows an absorbance maximum at 125 nm. Absorption maxima due 0.0 > o transitions are not seen in typical UV-Visible spectra (200 - 700 nm) Transitions in which non bonding electrons are excited to o” antibonding molecular orbitals are called n-> 0” transitions, Saturated compounds containing atoms with lone airs (non-bonding electrons) are capable of n ~» 6" transitions, For example, alcohol, ethers, amines, alkyl halide etc, These transitions usually need jess energy than o—>° transitions. | | n~ 0° Transitions | n—> x’ Transitions When electrons present in non bonding orbital are excited to x” orbitals, the transitions are called n>" transitions. All organic compounds containing double bond between carbon and some heteroatom (O, S, N etc.) show this transition, >" Transitions Transitions in which a x electron is excited to x* orbital are called x > n" transitions. This pe of transition occurs in unsaturated compounds (alkenes, alkynes, waver compounds). Most absorptionfall in an experimentally convenient region of the spectrum (200 - 700 nm), These ‘tansitions need an unsaturated group in the molecule. Transitions involving charge-transfer electrons ‘hese transitions occur mainly in inorganic complexes formed by coordination of ligands {O metal atom. The transitions involve electron transfer from one part OT Me Sorte to aother. More specifically, an electron moves from an orbital that is mainly ligand in character to one that is mainly metal in character or vice versa. These are intense absorptions. Some examples of these absorptions are permanganate ion, dark colour of Ir ~ benzene solution. Transitions involving d and f electrons The electronic spectra of transition met refer es i ause the) involve orbitals whic! inly metal-d in character: The spacing between the ener; levels depends upon the geometry of the complex, nature oF the ligand, oxidati f Jneialetc. Similarly, the absorption spectra of lanthanides and actinides result from f-f ‘ransitions. —— Peak Shape: UV and visible spectra of molecules consist of bands rather than peaks. In a molecule, the ‘toms can rotate and vibrate with respect to each other. These vibrations and rotations also have discrete energy levels, which can be considered as being packed on top of each electronic level as shown below. ‘Therefore in molecules, each electronic state is associated with a number of closely spaced vibrational sub states and each vibrational state has a series of closely spaced rotational levels. In principle, electronic «excitations can occur from any vibrational sublevel of the ground electronic state but these generally occur ‘fom the v, level of the ground electronic state because this is the highly populated state for molecules at Foom temperature, As a result of these transitions, the absorption spectrum of the molecule in vapour state would contain a large number of closely spaced lines which can only be separated with the help of instruments of high resolution. However if the spectrum is taken in solution state, this fine structure is senerally not observed because of solvent-solute interactions which tend to smooth cout the spectrum into bands. Thus UV and visible spectra of molecules consist of bands rather than peaks. 3 Z & 5] Rotational Vibrational 5] electron levels electronic levels — SaaS EySelection Rules for electronic spectroscopy Both atomic and molecular spectra result from the transition between different energy levels. These transitions take place between certai cific energy levels and do not take place benteerany io onergy levels, Thera heeit transitions can take place. The ‘restrictions thus applied on Tariton ar ealed suelo ae ps a ke ae by Be selection mules is known as allowed transition’ were as that not penmiuel ig called forbidden transition For a molecular electronic transition, the selection rules are as follows. | Transition which does not involve change in spin quantum number is allowed transition i.e. AS = 0 i.e. singlet-triplet transitions are forbidden, 2. Only one electron is involved in a transition, 3. ‘The transitions between orbitals of different symmetry can only occur (-» u and ug allowed; > wot allo’ The allowed transitions Fave high value of emux (extinction coefficient), generally more than 10°. An example of allowed transition is 3 > 4° transition. However forbidden transitions can also take place, but its probability is low. égasfor such transitions lies between 10-1000. The »—> x" transitions are forbidden but Bive rise to ‘weak absorption, For example, benzophenon shows two absorption bands in UV spectrum, @ Awe 252 nm, Emax 20,000 (allowed) i) Ana 325 1m, Emae 180 (forbidden) Inn=2:t' transition, both rand x" orbitals lie in the same plane and hence over! ese_orbitals in excited state is quite large. Asa result “wanstions are highly probabte——On the other handy ow transitions are symmetry forbidden because n electrons on the heteroatom are in a plane perpendicular to the n° MO. Since the regis of spece ofthese two orbitals Overlap poor ike epee “exGifation of n electron to 7” orbital is low. Though symmetry forbidden, this transition Cccurs due to viberational interaction and twisting of molecule. in excited state, it becomes partially allowed. Beer-Lambert law Many compounds absorb ultraviolet (UV) or visible (Vis.) light. The diagram below shows a beam of monochromatic radiation of intensity 4 direcred at a sample solution, Absorption takes place and the beam of radiation leaving the sample has intensity I. Diagram — of Beer-Lambert absorption of a beam of light as it travels through a cuvette of size I hLambert investigated the relationship between the intensity of incident light Jp and that of tansmitted light J, . Lambert law states that “The rate at which the intensity of light decreases with thickness of the absorbing medium is proportional to the intensity of the incident light.” -dVdx=ki or dV =-kdx where Is the intensity of incident light, x isthe thickness of gOsorbIng TACHI And k is a constant called absorption coefficient of the medium for light oF @ particular wavelength. ‘The negative sign indicates that I decreases as x increases. On integrating the above equation between I = Ip (incident light) to I = i (transmitted light), we get 4 xl Jai = -Skax 4 x0 In Wp = -K1 : Taking antilog WI, =e"! or =e“ Beer's law states that ual fictions ofthe incident radiations are absorbed by layers of solution with equal cohcentrations and same thickné ‘On combining the two Taws, Beer-Lambert law states “On passing through a solution, rate of decrease of intensity of incident monochromatic radiation with thickness of the solution is proportional to the intensity of incident light and concentration of the solution.” So,-dlidx=k'le where ¢ is the molar concentration of the solution, k’ is molar absorption coefficient. On integrating, the equation between I = I, (incident light) to I = I, (transmitted light), we get In Wy = -k’le or WIp=e*"* ete fo. 10 #19308 Substituting k’/2.303 = we get lo“ § snow absorption coefficient or molar absorbtivity with units of Lmdt" cm". The equation can be written as ~log Il, = eel or log If = ecl Put logl/k=A So, A= eel Ais the absorbance or optical density and has no units. — — of how strong ‘The molar absorptivis ar extinction coefficient ¢.of a che fes-ata given wavelength is ‘eu fiw seme pe absorbs light at that iit Itis an intrinsic erty of the species; the ackial absorbance of a samplé is dependent on its “thickness [and tie aon rhe species, The amount of radiation absorbed may be measured as Transmittance. Transmittance is defined as the intensity of transmitted light to that of ineident ight‘Transmittance, 7 = [,/ 1, % Transmittance, %T = 100 T The relationship between absorbance and transmittance is illustrated in the following diagram. ‘% Transmittance Absorbance So, if all the light passes through a solution without any absorption, then absorbance is Zero, and percent transmittance is 100%. If all the light is absorbed, then percent transmittance is zero, and absorption is infinite. depends on the total quantity of the absorbing compound ite. If we plot absorbance against concentration, we get a straight line passing through the origin (0,0). htabtan Note that the Law is not obeyed at high concentrations. This deviation from the Law is not dealt with here. Concentration Numerical Problems on Beer-Lambert law ose in equiti 1. What is molar extinction’ coefficient ofa solute which absorbs 90% of a certain ‘wavelength of light beam passed through 1 cm cell containing 0.25 M solution? 2. Light of definite wavelength was passed through a cell of 4 em thickness containing 0.02 M solution of a given substance. If molar extinction coefficient is 3+ Determine the transmittance, absorbance and molar extinction coeflcien ofa coition Which transmits 50% of a monochromatic light when passed through 1 om thick cell containing 5 X 10 M of solute, Ultraviolet-visible spectrophotometer The instrument used in Uliraviolet-visible spectroscopy is called ultraviolet-visible SPeetrophotometer. To obtain absorption information, a sample is placed in the Spectrophotometer and ultraviolet or visible light at a certain wavelength, or range of 10 @® wen sol sof. Saiuent form Corben ovking vnotocuh. Oi or aoe ese tahwavelengths, is transmitted through the sample. The spectrophotometer measures how much of the light is absorbed by the sample. The intensity of light before going into a certain sample is symbolized by Jp, The intensity of light remaining after it has gone through the sample is symbolized by J. The fraction of light transmittance is (J / 1), which is usually expressed as a percent Transmittance (%T). From this information, the absorbance of the sample is determined for that wavelength or as a function for a range of wavelengths. Sophisticated UV/Vis spectrophotometers often do this automatically. Although the samples could be solid, or even gaseous, they are usually liquid. A transparent cell, often called a cuvette, is used to hold a liquid sample in the spectrophotometer. The pathlength Z through the sample is then the width of the cell through which the light passes through. Simple, economical spectrophotometers may use cuvettes shaped like cylindrical test tubes, but more sophisticated ones use rectangular cuvettes, commonly 1 cm in width. For just visible spectroscopy, ordinary glass-cuvettes may be used, but ultraviolet spectroscopy requires special cuvettes made of an ultraviolet-transparent material such as quartz. : ol diagram of the components of a typical spectrometer is shown in the following diagrn, The functioning of this instrament is relatively straightforward. A beam of light from a visible and/or UV light source is separated into its comp Ive ths by a. pwism or diftaction yrofing. Each monochromatic (angle svete oh) ten oe x’) 15,000 170 (@—> 2") 10,000 | 280 (n> n°) 165 (n> 0°), 190 (@ > x’) 5,000, 16,000 15, Ce-COOH 208 (n>) 2 -CONH? 220 (n> n') 63 71 -COOR 2i@on) | 37 | 201 (n> 0°), 274(n >) 5,000, 17 CN 165inon) 65 NEN 338 >) - 4 _ . —__| Auxochromes Groups which themselves do not show any characteristic absorption above 200 ‘nm but when attached to a given chromoy tion towards longer wavelength along with increase in intensity of the absorption. For example: on “Nf, -SH, “OR, “NHR, -NRz, -SR, halogens etc. For example, benzene shows an absorption band at Amar 254 nm with Emm Of 230. But aniline shows Anas at 280 with tay of 1430. This is due to conjugation between gitrogen nonbond 3 electrons. However, if a proton gets attached to aniline and forms NH3* then the absorption of resulting anilinium ion is observed at 254 nm because now nitrogen’s lone pair is not conjugating the ring m electron density. Another important fact to remember is that auxochromes shift the absorption of. —>n” transitions towards longer wavelength whereas reverse effect is observed for n— x transitions (as discussed in following sections). Nt “ty fee cere | coonm © ces Te 230 1420 i Q Q, Q. By \\—on \ Ny ee Hye aoe Hc HC HC’ Imus 298 208 214 295 Fig. 1‘The absorption band is affected in four different ways. 1. Bathochromic shift or Red shift 2. Hypsochromic shift or Blue shift 3. Hyperchromic effect 4. Hypochromic effect Bathochromic shift or Red shift The shift of absorption maxima to longer wavelength is called bathochromic shift or red shift. This can be achieved by (i) attaching an auxochrome to a carbon ~ caibon double bond or to benzene ring as discussed above (ii) conjugaticn of two chromophores (iii) decreasing of polarity of the solvent. All these factors bring about decrease in energy di e ital i i sition. ypsochromic shift or Blue shift : A shift in absorption maxima to shorter wavelength is called Hypsochromic shift or Blue shift. This can be achieved by ( Attaching auxochrome to the C=O (carbonyl) group. For example, n> 2° ansition of acetaldehyde appears at 293 nm (¢ = 12) but it shifts to 235 (c= $3) if H is replaced by Cl. Similarly, Ama for acetamide, ethyl acetate and acetic acid appear at 214 nm («:« 63), 204 (¢ = 60) and 204 (¢ = 32) respectively (Fig. 1). This may be due to more: decrease in the energy of n orbitals compared to x" orbitals, caused by ~I causing lone pair of carbonyl to be held more strongly. fi) Increasing the polarity of the solvent. For example, » —> x" transition of acetone in effect of heteroatoms (O, N, Cl). These atoms withdrats hexane appears at 279 nm and at 264 nm in water. Tais is because H bonding lowers'\ the energy of n electrons and thus increases the energy gap between the two orbitals. Hyperchromic effect This effect leads to an_increase_in_molar_ absorptivity. Red shifi is generally accompanied by hyperchiOmie effect Hypochromic effect This effect leads to decrease in molar absorptivity. Blue shift is generally accompanied by hypochtomic effect. Solvent Effects longer or shorter wavelength. For different type of transition, the effect is different, (i) n-> x" and n-> o" transitions generally shift towards lower wavelength if polar solvent is used. This is because the n electrons are relatively more stabilized in the ground state due to hydrogen bonding or dipole - dipole interactions with polar solvent than in excited state. As a result, the energy difference between ground and excited state increases resulting in shift towards shorter wavelength. It is to be noted that greater the shift, stronger the H bonding. The extent of H bonding decreases in the order: water > methanol > ethanol > chloroform. Xmax for n> x’ transition of acetone appears at 279 nm in hexane (non polar) and shifts to shorter wavelength as the polarity of solvent increases, Solvent CHC, GH;OH —-CH;OH H,0 max (nm) 27 2 270 264.5 . b The polarity of a solvent usually shifts the position of an absorption band towards ey A Se. { BS bee To give Wintte D gee” ma ificreases. (ii) x > m transitions shift to longer wavelength as the polarity of solvent, This is due to the fact that x” state, being more polar in nature than m state, (which is almost non polar because electrons are evenly distributed on two atoms involved in = bond formation) is more stabilized on interaction with polar solvent than the ground state, Effect of Conjugation When the TWO chromophoric groups are conjugated, a large effect on the spect is produced because the 1 electron system is now spread over at least four atomi snters. As a result, the high intensity absorption band due to ~ n* transition is ied by 15-45 nm towards longer wavelength with increase in intensity (red shift and hyperchromic effect). Similarly, if carboayl group conjugates with double bond, absorption bands due to both x — xe and:n =n transition shift to Tower wavelenati UY spectra of Dienes Alkenes such as ethylene absorb at 175 nm (¢ = 15,000). But when two double bonds conjugate as in 1, 3 - butadiene the absorption band shifts to 217 nm (¢ = 21,000). This may be explained as follows. According to molecular orbital theory atomic p orbital on each of the carbon atoms combine to make two = molecular orbitals (Fig. 7.11). The two electrons forming x bond are filled in the Jowest orbitals designated as y! in the Fig. Now consider 1, 3- butadiene, which has four atomic p orbitals and four p electrons (each contributed by each one of the carbon atoms of butadiene) that form x system of two conjugated double bonds. The four atomic orbitals combine to form four molecular orbitals as shown in Fig. 7.12. ‘The highest occupied MO (HOMO) here is designated as y2 as shown in the fig. The ‘energy difference from y2 (HOMO) to y3* (LUMO) is lesser in energy compared to that of y1 and y2* of ethylene. The transition for diene is thus involves lesser energy compared to that of ethylene (red shifi). More over greater the number of conjugated double bonds, greater is the red shift. Moreover the energy difference between HOMO and LUMO becomes progressively smaller with increasing conjugation The effect is similariy observed in homoannular dienes (two double bonds in a ring) and heteroannular dienes (conjugating double bonds in different rings). CHa bute tya-diews d max a —— 72 Cte mA oyneund LOMO nt n ura -t)3, "R21 OF Olutocabization = aes Hom onne hore ~ig,¢-tiene 258 te. x Sn —«ae = HCH Cnc In cien an5 TS taoas* NOMEN ery an hese fe =e 6UY Spectra of unsaturated ketones: enones The UV spectra of unsaturated carbonyl compounds in which the C=C and C=O are not conjugated are simple summation of the absorption of the ethylene and carbonyl chromophores. In ethylene the absorption occurs at far UV region (175 nm) and is due to 1+" transition which being symmetry allowed is intense. An isolated carbonyl group gives two absorption bands [190 (n> n'), 280 (n> n')}. The band at 190 nm is generally not observed as it lies below the cut off limits of the solvents. The other at 280 rom, though weak, lies much above the solvent cut off and is generally observed. However when the C=C and C=O chromophores are conjugated (enones), both x» 1° and 1 ~> x” transitions shift towards longer wavelength (red shift). In this case, an intense absorption band in the region 210 — 250 nm is observed due to x —> x" transition and a weak absorption is observed at 310 330 nm due ton -> 2 transition, (Fig. 7.16)Applications of UV spectroscopy 8 tection offfunctional UV spectrosSopy has been used to detect the presence or absence of certain fanctional groups in organic molecules. For example, if ¢ molecule doe not show absorption above 200 tun, it can be inferred that no conjugated chromophore, aldehyde, Ketone, aromatic group is present \Distinction between Coalugated and non conjugated compounds can be made on the basis of observed Amar: _Qiiantitative Analysis ' Due to high sensitivity UV Visible spectroscopy is a valuable analytical tool. By using Lambert Beer law, (A = ecl) which relates absorbance with concentration, quantitative analysis can be performed for compounds which show absorption in this region. fentification \f geometrical isomer? Generally geometrical Tsomers absorbs at different wavelength. This fact is employed to distinguish between cis and trans alkene isomers. Trans. isomers abet at longer Zavelensth. Row for trans ~ sttbene is 294 nm and for cis ~ stilbene itis 278 nm tection of impurities Impurities-“Wwhieh absorb in UV region, can be detected from the UV spectra. A practical application is the detection of benzene even if present in low conventiation tn ¢ sample of gthanol: Benzene absorbs at 254 nm where as ethanol does not abents above 200 Similarly, impurity Profiling Of Various drugs is done by using this technique. a Detection of formation of charge transfer complexes Many electron rich organic molecules such as aromatic hydrocarbons, phenols, aromatic ampes form charge transfer complexes with electron deficient molestie ack as pieric rh —™——<“—sre—Sss———————— from the Gonor to the acceptor resulting in strong charge transfer absorptions, Monitoring progress of a reaction UV spectra help in mo: mal amount of solution taken fiom reaction mixture at different interes we the reaction. For example, reduction of a ketone to alcohol can he monitored by analyzing the n-x* transition of ketone. The absorption_band_teduces_in_intensityand_confirms the completion of the reaction if disappears completely.Vibrational spectroscopy The vibrational spectra result from the transitions of electrons between vibrational energy levels. Since the frequencies absorbed due to these vibrations are observed in infrared region, it is also known as Infrared spectroscopy. AIT compounds containing Zovalent bonds may absorb in infrared region of electromagnetic spectrum. In contrast to ‘an UV spectrum, an IR spectrum contains a number of peaks which provide a wealth of information about the structure of the compound. The position of an absorption in IR spectrum is generally expressed in the form of wave number, V. The units are cm”, The IR region extends from 12,500 to 50 cm’'. However, the region of 12,500 to 4000 em is known as near infrared region and that from 400 to 50 om’ is called far infrared region and these regions are seldom usetl for spectroscopic applications. The region of interest is, therefore, from 4000 to 400 cm"! because most of the organic ‘compounds absorb in this region. Energy of a diatomic molecule and Simple Harmonic Oscillater Model In order to understand the principle underlying the vibrational spectroscopy, consider the bond formation for a diatomic molecule. When two atoms come closer to form a stable covalent bond, there is attraction between the nucleus of one atom and the « electrons of the other atom and vice versa. On the other hand, there is repulstorr between —— the positively charged nuclei of both atoms and between negatively charged electron clouds of the atoms. The two atoms setile at a mean internuclear distance (eq) such that these repulsive and atiractive Torces are just balanced and the total energy of the whole system is a minimum. Squeezing the atonis more closely will cause repulsive forces-to~ fise rapidly, while pulling them apart is resisted by the attractive force. Any attempt to diston the bond length requires an input of energy and we may plot the energy against inter nuclear distance. Fig. 1- Molecular. potential energy QL curve X(biwe—Hw) can be approximated by a parabola (ew. JI Fine) near the bottom of the well. On x axis is inter nuclear distance and y g I axis represents potential energy of a the molecule. The distance up to green mark represents req (bond length).Now, imagine Pushing the two atoms closer, which would lead to compression of the bond and therefore decrease in bond length then ‘eq. Similarly if two atoms are pulled apart, the bond would experience extension and internuclear distance would be. greater than freq. These situations will lead to increase in Potential energy of the molecule. Greater the deviation from Teq during such o: lations, higher is the potential energy of the Where pis reduced mass and is given by y = mima/ my +m; my and m2 being niasses of the atoms forming bonds. allowed vibrational energies for a system have been calculated by solving chrédinger wave equation for simple harmonic eacillens and the energy of a vibration is then given as (is the number of vibrational energy level) we get Thus energies associated with these levels are also If is equal to zero then E, = ¥%4 ho, So even at energy is ed by the ce vibrational levels can be obtained by, putting v equation 2 or 3. It is obvious that the difference between any two consecutive energy levels is same because y can have integral values, Anharmonicity ‘The energy levels Es, Es, E>, E3_calculated from the equation 3 given above by putting v= 0, 1, 2, 3.... are only “poroximate because they are based on the parabolic approximation (red line, Fig. 1) to the actual Potential energy curve (blue line). Realmolecules do not obey exactly the laws of simple harmonic motion because real bonds, though elastic, are not so homogeneous as ta obey Hooke's law. If a bond betwe=r atoms is Stretched beyond a ceriain limit, the molecule dissociates into atoms. Hence though for small amount of compressions and extensions the bond may be assumed perfectly elasie, for larger amplitude, the behavior deviates from that of a simple harmonic escllaton and then motion becomes anharmonic. A purely empirical expression which fits the actual potential energy curve (blue line) was derived by P.M. Mot i i V = Daal 1-exp a(Fog-1)? Deq is the depth of the Potential energy curve and is called dissociati is a constant for a particular molecule. Shape of a Morse potential energy curve is shown here. The lines inside the curve représent different vibrational levels vo. ¥;, ¥2 and so on. Then vibrational energies of these levels can be found from the ‘equation Ev = (V+ b)htde - (0+ He) Pheer @, is the frequency of vibration and x, is anharmonicity constant. Dey The number of energy levels in Morse oscillator is finite vo, vy Va Yam The second term subtracts from Inter nuclear the first, so gives convergence to distance the Tevels at higher quantum numbers so difference in these energy levels decreases Progressively. Unlike the harmonic oscillator, excitations can occur from levels vy —» v4, vo —pv2, vo—> v3 EnergyFundamental Vibrations Consider a molecule containing N atoms. We can refer to. the position of each atom by specifying three coordinate values (x, y, z in Cartesian coordinates). Thus the {otal number of coordinate values is 3N. We can say the molecule has 3N degrees of freedom since each coordinate valué 1s expressed independently of the other. Now the molecule is free to meve in 3D space without any change§in shape. We can refer fo such movement by noting the position of its centre of gravity at any inctant and to do this three coordinate values are stated. This translational movement. therefore, uses three degrees of freedom out of the total 3N- Further. The Tolation oT > non Tinéar molecule can be resolved into components about three perpendicular axes. Specifications of these axes also require three degrees of freedom. So, if we subtract three translational id three rotational degrees of freedom from total 3N, a non lin molecule. Hence a molecule with N atoms has 3N-6 vibrations. On the other hand, if the molecule is linear, there is no rotation about the bond axis of the molecule. Hence only two degrees of rotational freedom are required leaving 3N-5 degrees of vibrational freedom (one more in this case than non linear molecule). 3N-6 (for non linear molecule) or 3N-5 (for linear molecule) vibrational degrees of freedom are called Fundamental Vibrations of the molecule. : ‘Types of Fundamental vibrations There are two types of fundamental vibrations for molecules ~ stretehit bending. come aitstretching vibrations, the distance between the atoms decrease or increase bat atoms remain in the same bond axis during vibration. On the other hand, in bending vibrations, the positions of atoms change with respect to original bond axis More. eneizy-is required to_stretch a bond than to bend a bond. Therefore, absorption bands due to stretching vibrations appeaF ier Trequency (or wave number) than those due to bending of the same bond. There are two types of stretching vibrations. (@) Symmetric stretching A stretching vibration is said to be symmetric if all the bonds are simultaneously stretched or compressed. It is denoted by v,. (©) Asymmetric or antisymmetric stretching A vibration involving stretching of one bond and compressing of the other is called asymmetric or antisymmetric stretching and vice versa. It is represented as Us Generally vaym stretching requires higher energy than vam. For example, Um for HL0 appears at 3756 cm” and v, appears at 3652.em". Similarly, for CH, BrOUP, vag appears at 2926 cm’! and v, appears at 2853 cm’, 1g and Bending vibrations are also called'deformations. These are of two types. 1. In plane bending vibrations During these vibrations the two atoms remain in the same plane of the molecule. These are further of two types 4(a) Jn plane scissoring deformations. The two atoms move towards each other like blades of scissors. (b) In plane rocking deformation. The two atoms move in same direction, first to one side and then to the other side. 2, Out of plane bending deformation In this vibration mode, the two toms move out of the plane of the molecule. “These are again of two types. (a) Out of plane wagging deformation. In this bending mode both the atoms sinwultaneously move above and below the plane with respect to central atom. (b) Out of plane twisting deformation. When one atom moves above and the other below the plane of the molecule with respect to the central atom, vibration is called out of the plane twisting. x Asyemeviont Symmevice! Zeerehing ‘Brething Goons (wens Swetching wbrat‘ons x Inplane bending ‘oucet-plane bending redszoring ‘or wagging eon (eons (> \ ~ ‘Ouot-plene bending plane bending ‘oetwistng ‘or recing fecHy @eHy Bending vretions Various values for CH vibrations are given as under. Vas 2926 om”; v, 2853 cm”; 8s 1465 em"; @ 1250 em"; t 1250 em”; p 720 em™ Three fundamental vibrations for water are (a) vss 3756 om" (b) v, 3652 om"! (©) 8 1595 cm"Principle of IR absorption and selection rule Not all the possible vibrations within a molecule will result in an absorption band in infrared region. For a vibration to appear in the IR spectrum. it must be accompanied by change in dipole moment during the vibration, Most of the molecules possess dipole moments due to the presence of polar covalent bonds linking various atoms. When a polar covalent bond undergoes a stretching vibration along inter nuclear axis o1 sharing a common atom undergo a bending vibra a s i i is luced. Interaction of this oscillating dipole moment and electric vector of IR radiations lead to abe energy from the radiations. This interaction and hence absorption can occur only ifthe dipole moment at one extreme of vibration is different from the dipole momen 4 other extreme if the vibration. Hence. selection rule for IR spectroscopy states that only those” vibrations, which are accompanies ein dipole moment will absorb in the TR called IR active vibrations. Those vibrations which arenot ipole moment are called IR ‘inactive vibrations” aE EN inactive vibrations show absorption band in teTR Spectrum, infrared absorption is observed, as these molecules have zero dipole stretching or compressing of ‘the bonds will heteronuclear diatomic molecules such as CO, HCI, moment, infrared activity occurs because moment (since dipole moment = ch: {tis not Wecessary Tora tomipourid to Fave permanent dipole moment to be IR ee ,——r— does Pot have @ permanent dipole moment. Since the molecule is linear, i hog 3N-S fundamental vibrations i.e. 4 vibrations as shown below. ea SO GS- —- @wOwe- A B Spee epee! one eee, furan the oxtof plane mode ts to place circled + or ~ signs on the atoms, signifying motion above of below the plane of the paper, respective. - nese vibrational modes, shown above, are responsible for the "greenhouse" effect in ich wi iated from the earth is absorbed (trapped) 6 CO} molecules in the Smosphere. The arrows indicate the directions of motion. Vibrations labled and B —— ‘aid G0 ~___ This means, for-romonuclear diatomic molecules such as Hz, N2, Op etc. ne 2t0_dipole_ moment andrepresent the stretching of the chemical bonds, one in a symmetric (A) fashion, in which bath C=O bonds lengthen and contract together (in-phase), and the other in an asymmetric (B) fashion, in which one bond shortens while the other lengthens. The symmetric stretching (A) of CO is centrosymmetric soit is not accompanied by change in dipole moment and hence IR inactive, so this vibration“is not observed in the infrared arst-COs, Incase of asymmetric (B) stretching a dipole moment_will_be periodically produced and destroyed resulting in-a-ehange in dipote moment and therefore Tativity. To be “active” means that absorption of a photon to excite the vibration’ is allowed by the infrared "selection rule” stated above. Infrared radiation at 2349 em! ‘xeites this particular vibration. Same is the situation with bending vibrations. The ‘wo equal-energy bending vibrations in CO (C and D in Figure) are identical except that one Bending mode is in the plane of the paper, and one is out o! the plane. Infrared radiation ch a . at 667 © ‘excites these vibrations. Such absorptions are called degenerate. To studens: Show diagrammatic representation of dipole moment produced or destroyed as the vibrations in CO; take place. It has been observed that the predicted number of hands AR spectrum of a molecule. The reasons are 1, According to the selection rule the necessary and sufficient condition for a fundamental vibration to appear as a band in the IR spectrum is that it must be accompanied by change in dipole moment during vibration. Thus symmetric molecules show lesser number of bands. Example, C = C stretching vibration of ethylene does not show absorption bands in the spectrum of ethylene: 2. Very weak absorptions or those arising ata position outside the region 4000 - 400 cm’ are generally not recorded. 3. Closely spaced absorptions may overlap. 4 Absorptions die to overtones, combination or difference bands also appear which change the number of absorption bands than predicted. seldom observed in the ‘Overtones These appear at twice or three times the wavenumber of fundamental vibrations and are 10 — 100 times less intense than fundamental vibrations. These are observed due to Ve —> V2 and Vo —> Vstransitions. Aromatic compounds show such bands in the region 1667 — 2000 cm". . Combination bands These bands appear at the sum of the wavenumber of two fundamental vibrations. Veomb = vi + V2 Difference bands appear at a wavenumber corresponding to difference in ‘wavenumber of two fundamental vibrations. These are weak bands. vair= v1 - V2 Another effect which enhances the intensity of weak bands is Fermi resonance Fermi resonance If the energy of a fundamental vibration lies close to that of an overtone or combination band, the transfer of energy occurs from fundamental vibration resulting in the increase of intensity of overtone or combination band. This type of #coupling between fyndamental vibration and overtone or combination band Fermi resonance, It is\generally observed in the spectra of earbonyl compounds called Position of absorption bands can be predicted by taking into account the following factors. ‘ 1. Strength of bond: It evident from Hoake’s law that epends upon the force consfant and hence strength of a bond. Strong he frequency of absorptiork Strength of bond in in the order Single bond < double bond < triple bond as is shown here for certaif tripie/double/single bonds. : C= C.C EN (2300-2000 em): C = C.C =0.C =N ee } C= C.C =O. C = N (1300-800 cr). / 2, Masses of the atoms: Lower the masses of the atoms forming bond? higher is the frequency. O-H vibration appears near 3570 em’ where 4s O-D absorbs around 2630 cm". / However both thé factors mentioned above should be considered together to predict the absorption frequency for a vibration. One of these factors may dominate the other and show remarkable effect on the frequency of absorption. For example, the masses of CH, NH. OH. HF decreas the order €-H > N-H > O-H > H-F whereas their force constants (or bond strength) are in the/reverse order C-H < N-H < O-H < H-—F. The absorption due to H-F stretching vibrafion appears at 4138 cm’! and those due to O-H, N-H and C-H appear at 3570, ce 3000 cm" respectively. dug;to a vibrition we bond, higher d 3,Type of molecular vibratien: The frequeriyy of IR absorption band depends upon the type of vibration As stated already, stretching vibrations of a group require more energy as compared to the bending sof saine group. More over asymmewis sireiching “appear at E gher Wequency than Mar oF somone ztching of same group. Similarly among various ben ing deformation appears at higher frequency than ‘wagging and twisting deformations. See;absorption: frequencies for CH, group. Structural factors affecting vifrational frequencies towards lower frequency. Due to/hydrogen bonding length of OH or NH bond increases, that is, the bonds are weakened So, lesser the strength of bond, lower is the frequency of absorption. Further, stronger /the hydrogen bonding, greater is the downward shift. Intermolecular hydrogen boyding gives broader band while intramolecular hydrogen bonding gives sharper bandy. Example, Free OH groupé in alcohols and phenols absorb\at 3650-3600 cm", Their concentrated solutions give broad band at 3400-3200 em" due to intermolecular hydrogen bonding. In vapour phase or dilute solution in non pol Sz, band appears at tHe position of free OH group (3650-3600 exist in monomeric State in dilute solution and absorb at 17 stretching. In conceftrated solutions or in solid state they exist stretching appearsAt 1710 cm”. Also OH stretching vibrations in 3600 cm’ (in freg‘acid) to 3400 cm’ or lower if in dimeric state. Hydrogen bonding causes shift ‘ IR absorption bands due to OH and NH vibrations dimmers, so C=O. acids shift from