Introduction The term "infra red" covers the range of the electromagnetic spectrum between 0.

78 and 1000 mm. In the context of infra red spectroscopy wavelength is measured in "wavenumbers" which have the units cm!1. wavenumber " 1 # wavelength in centimeters

$ It is useful to divide the infra red region into three sections% near mid and far infra red% $ RegionWavelength range &mm'Wavenumber range &cm!1'(ear0.78 ! ).*1)800 ! +000,iddle).* ! *0+000 ! )00-ar*0 !1000)00 ! 10 $ The most useful I... region lies between +000 ! /70cm!1.

$ Theory of infra red absorption $ I. radiation does not have enough energy to induce electronic transitions as seen with 01. 2bsorption of I. is restricted to compounds with small energy differences in the possible vibrational and rotational states.

$ -or a molecule to absorb I. the vibrations or rotations within a molecule must cause a net change in the dipole moment of the molecule. The alternating electrical field of the radiation &remember that electromagnetic radation consists of an oscillating electrical field and an oscillating magnetic field perpendicular to each other' interacts with fluctuations in the dipole moment of the molecule. If the fre3uency of the radiation matches the vibrational fre3uency of the molecule then radiation will be absorbed causing a change in the amplitude of molecular vibration

$ Molecular rotations $ .otational transitions are of little use to the spectroscopist. .otational levels are 3uanti4ed and absorption of I. by gases yields line spectra. 5owever in li3uids or solids these lines broaden into a continuum due to molecular collisions and other interactions.

$ Molecular vibrations $ The positions of atoms in a molecules are not fixed% they are sub6ect to a number of different vibrations. 1ibrations fall into the two main catagories of stretching and bending.

$ Stretching: 7hange in inter!atomic distance along bond axis

$ Bending: 7hange in angle between two bonds. There are four types of bend8 $ .oc9ing $ :cissoring $ ;agging $ Twisting

$ Vibrational coupling In addition to the vibrations mentioned above interaction between vibrations can occur &coupling' if the vibrating bonds are 6oined to a single central atom. 1ibrational coupling is influenced by a number of factors% $ :trong coupling of stretching vibrations occurs when there is a common atom between the two vibrating bonds $ 7oupling of bending vibrations occurs when there is a common bond between vibrating groups $ 7oupling between a stretching vibration and a bending vibration occurs if the stretching bond is one side of an angle varied by bending vibration $ 7oupling is greatest when the coupled groups have approximately e3ual energies $ (o coupling is seen between groups separated by two or more bonds

$ SE E!TI"# R$ E 8 $ :<=<7TI>( .0=< 1' 2?:>.@TI>( >- 7>..<7T ;21<=<(AT5 >- .2BI2TI>( &,2T75I(A >-.<C0<(7D 2 molecule will absorb suitable radiation when its natural fre3uency of vibration matches with the fre3uency of incident radiation &i.e. a net transfer of energy ta9es place and it results in a change in the amplitude of molecular vibration' (atural fre3uency of 57l molecule is 8.7 E 101F54&vib#sec'or&)8G0 cm!1' ;hen I. radiation will allow to pass on 57l sample and transmitted radiation is analy4ed .It is observed that part of radiation which has same fre3uency 8.7E101F 5H is absorb. Thus remaining has been transmitted so gives characteristic value of 57l

$ %& 'I(" E M"ME#T 8 $ )' BI@>=< ,>,<(T I2 molecule will absorb I. radiation if the change in the vibrational state is associated with the change in the dipole moment of the moleculeJ K " 3 x r 2 dipole moment arises from a separation of charges in a molecule 8 K "dipole moment &7oulomb Lmeters' 3 "magnitude of charges r "vector going from Mve charge to Nve charge

$ SE E!TI"# R$ E ") VIBR*TI"#* +$*#T$M #$MBER 8 $ F':<=<7TI>( .0=< >- 1I?.2TI>(2= C02(T0, (0,?<. ?ased on the harmonic oscillator model &Ov " P1' 5ere N absorption Q ! emission or 1ibrational 3uantum number change by unity

5armonic oscillator 2nharmonic oscillator >vertones and fundamental band :o far as harmonic oscillator model is consider the lower vibration state can be explain &v ! vR"1' but for higher vibrational state the selection rule may fail because vibrational energy levels are less separated as the vibration state increases &?ut for harmonic oscillator model it is not true ' >vertones and fundamental band can not be explain by 5armonic oscillator model. :o vibrational diatomic molecule can be explain well using anharmonic oscillator model 2nharmonic oscillator model can explain the selection rule for all transition . -or real molecule they donSt obey simple harmonic motion. ?ecause the bonds are also real Therefore anharmonic oscillator model consider Therefore energy difference goes on decreasing as 3uantum no. increasing Ov " P1 P) PFTT &overtone lines' is possible but they are having extremely low intensity. This are 9nown as overtones &they are wea9er'

$ they found that when a ball was suspended on a spring from a hori4ontal wall the fre3uency of vibration or oscillation n depended only on the mass of the ball and the stiffness of the spring. The term 2 is a constant of the proportionality. ?y varying the mass of the ball and the stiffness of the spring they were able to uncover the following simple relationship between fre3uency mass and force constant8

$ :uspending a ball and spring from a hori4ontal surface is a special case of the more general situation when you have two more comparable masses attached to each other. 0nder these circumstances when two similar masses are attached to a spring the relationship between fre3uency of vibration mass and force constant is given by8

where m represents the product of the masses divided by their sum &m1m)'#&m1Nm)'. This latter term is found in other physical relationships and has been given the name the reduced mass. It can easily be seen that e3uation ) is a special case of the more general relationship given by e3uation F. If we consider m1to be much larger than m) the sum of m1N m) m1 and substituting this approximation into &m1m)'#&m1Nm)' m). :ubstituting m) into e3uation F where m) is the smaller of the two masses gives us exactly the same relationship as we had above when the ball was suspended from a hori4ontal wall. The hori4ontal wall is much more massive than the ball so that the vibration of a smaller ball has very little effect on the wall. Bespite their simplicity e3uations ) and F play an important role in explaining the behavior of molecular systems. 5owever before we discuss the important role these e3uations play in our understanding of infrared spectroscopy we need to review some of the properties of electromagnetic radiation particularly radiation in the infrared range.

$ #umber of possible vibrational modes 8(umber of possible vibrational modes 72( ;< U(>; T5< @>::I?=< 1I?.2TI>(V D<: but howV F(!* for linear molecules F(!/ nonlinear molecules (8 number of atoms in a molecules ?0T ;52T I: F( * Q /. 5>;S: IT 7>,<V

$ 2toms are never fixed in the space but move about continuously <ach atom may be said to posses three degrees of freedom of movement and thus in (!atom &polyatomic molecule' ,olecule there will be F( degrees of freedom &That means F coordinates are needed to locate a point in space. 2nd each coordinate corresponds to one degree of freedom for one of the atom so a molecule containing (!atom is said to have F( degree of freedom '

$ -rom this F types of motion 1' T.2(:=2TI>( ,>TI>( 7orresponds to the movement of the entire molecule through space while the position of the atoms relative to each other remain fixed. In this sence the molecule may be considered as a single particle with the mass of the molecule located at its center of gravity and possesses three degree of translation freedom >. Befination of translation motion re3uire F coordinates and thus this common motion re3uires F of the F( degree of freedom

$ %&R"T*TI"#* M"TI"# 82nother F degree of freedom are needed to describe the rotational motion of the molecule. &i.e. poly atomic molecule has generally F degree of rotation freedom' ?ut in the special case of linear molecule all the atom lie on a straight line and only ) rotation can be define &because rotation around the bond axis is not possible' )'.>T2TI>(2= ,>TI>(

$ ,&VIBR*TI"#* M"TI"# 8(ow the rest i.e. substrate transition Q rotation motion from F( degree of freedom i.e. F(!/ & for non linear molecule' F of translation motion N F of rotational motion"/ Q F(! *&for linear molecule' F of translation motion N ) of rotational motion"* F'1I?.2TI>(2= ,>TI>(

$ (ow out of this normal vibration no. of stretching and bending vibration can be calculated -or stretching vibration "( !1 -or bending vibration ")( !*&non linear' i.e. W&F( ! /'!&( !1'X")( !* ")(!+&linear' i.e. W&F( ! *'!&( !1'X ")( M + <xamples8 >) () 7l)8 F(!* "Fx)!* " 1 only one vibration mode 7>) F(!* "FxF!* " +&linear molecule' 5)> F(!/ "FxF!/ " F

$ )*!T"R T-*T (R"'$!E' ESS #". ") (E*/S T-*# E0(E!TE' 8-27T>. T52T @.>B07<B =<:: (>. >- @<2U: T52( <E@<7T<B The symmetry of a molecular vibration result in no change in the dipole moment &i.e. in co) only ) pea9 out of +' The energy of two or more vibrations are identical &same or degenerate' The absorption intensity is so low as to be undetectable by means &detector' The vibration energy is in the w= region beyond the range of the instrument

$ I#STR$ME#T*TI"# :>0.7< :2,@=< .<-.<(7< T.2(:B07<. ,7 I#)R*RE' S"$R!E 8I(-.2.<B :>0.7< I. source consist of an inert solid that is heated electrically to a temperature between 1*00 and ))00 U The material is chosen so that its emission approximates 2s closely as possible to that of blac9 body radiator. &in candescent solid! the glow due to the great heat' ;e get continuum radiation approximating that of blac9 body results

;hat is this blac9 body radiationV It is truly continuum radiation is produced when solid are heated incandescence Thermal radiation of this 9ind which is called blac9 body radiation is characteristic of temp. of emitting surface rather than the material of which the surface is composed. ?lac9 body radiation is produced by the innumerable atomic and molecular oscillation excited in the condensed solid by thermal energy. It is clear that a very high temp. is needed for thermal excitation The maximum radiant intensity at this temp. occur between *000!*G00 cm!1 @roblems with Infrared from sun GGY of infrared rays are absorbed by water in our atmosphere 2t higher wave length the intensity fall is smoothly until it is about 1Y of max. intensity ?ut on shorter wavelength side the decrease is much more rapid 10000 *000 /70 cm!1 1 ) 1* Km

$ #u1ol mull $ 2 mull is a suspension of a solid in a li3uid. 0nder these conditions light can be transmitted through the sample to afford an acceptable infrared spectrum. The commercial sample of (u6ol or mineral oil which is a long chain hydrocarbon is often used for this purpose. ,ost solids do not dissolve in this medium but can be ground up in its presence. 2 small mortar and pestle is used for this purpose. If the grinding process gives rise to small particles of solid with diameters roughly the same as the wavelength of the infrared radiation being used )!* microns these particles will scatter rather than transmit the light. The effect of poor grinding is illustrated in -igures )G and F0 for a sample of ben4oic acid. If you find this type of band distortion with either a (u6ol mull or a U?r pellet &discussed below' simply continue grinding the sample up until the particles become finer.

$ The ma6or disadvantage of using a (u6ol mull is that the information in the 7!5 stretching region is lost because of the absorptions of the mulling agent. 2 spectrum of (u6ol is shown in -igure *. To eliminate this problem it may be necessary to run a second spectrum in a different mulling agent that does not contain any 7!5 bonds. Typical mulling agents that are used for this purpose are perfluoro! or perchlorohydrocarbons. <xamples include perchlorobutadiene perfluoro9erosene or a perfluorohydrocarbon oil.

$ 'ETE!T"RS 8B<T<7T>.: or T.2(:B07<.: There are F types of detector &transducer' 1' T5<.,2= B<T<7T>. )' @D.><=<7.I7 B<T<7T>. F' @5>T>( &C02(T0,' B<T<7T>. $ T-ERM* 'ETE!T"R 8T5<.,2= B<T<7T>. Thermal detector whose response depend on heating effect. ;hich in terns alters the physical properties of transducers such as resistance It is a transducer that changes thermal energy in to an electric signal. The electric signal is amplified and routed to the read out device

$ T-ERM"!"$( E 81'T5<.,>7>0@=< ,ost widely used I. detector 7onsist of ) pieces of metal such as I?iJ which are 6oined with dissimilar metal such as IsbJ &antimony' and form a pair of 6unction &) 6n' Zn. Is usually blac9ened &to improve its heat absorb capacity' ;ith blac9 metallic oxides >ne 6n between ) dissimilar metal is heated with I. radiation other 6n. Uept at const. temp..

$ @.I(7I@=< I2 752(A< I( T5< T<,@. 2T T5< ?>T5 BI--.Z(. ?<T;<<( ) 0(=IU< ,<T2= 720:<: 2( <=<7T.I7 @>T<(TI2= T> B<1<=>@< ?<T;<<( :@<7I<:J >r IB0< T> BI-.<(7< I( ;>.U -0(7TI>( >- ,<T2=: ;IT5 T<,@. 2 :,2== 1>=T2A< B<1<=>@ 27.>:: T5< T5<.,>7>0@=<J

$ This potential diff. is depend &proportional' to the amt of I. radiation falling on hot 6n. ;hole assembly is evacuated in still housing with I. transparent U?r window to minimi4e conductivity heat loss. 7apable to responding temp. diff. of 10!/ 9 corresponding to potential diff. of /!8 K1# K; 2dvantage that independent of response with change in wave length IT5<.,>@I=<J V

$ )' T5<.,I:T>. or ?>=>,<T<. ;hen irradiation by I. beam produced an increase in resistance of the metal strip which measured with a whetstone bridge 2 potential diff. between the ) elements produced a proportional voltage difference

$ ,&(#E$M*TI! 'ETE!T"R or 2" *3 'ETE!T"R 8F'@(<0,2TI7 B<T<7T>. or A>=2D B<T<7T>. @neumatic detectors respond to change in vol. of non absorbing gas or li3 with temp. change In pneumatic device if gas is used as medium called golay detector 5ere the absorbing radiation heats an inert gas &usually xenon' in a pneumatic chamber behind the plate and cause the gas to expand 2s the gas expands the flexible diaphragm at the opposite end of the chamber from the metallic plate is pushed outward

$ *pplications of IR Spectroscopy to Inorganic Molecules. ,any so!called inorganic compounds are in reality largely organic and for these we loo9 for the same functional group bands in the I. as we do for purely organic compounds. 5owever the infrared spectra of relatively simple purely inorganic compounds containing only a few atoms!!specifically inorganic salts containing polyatomic &complex' ions!!are 3uite distinctive and can be used to rapidly identify the ions. 7onsider a simple inorganic salt such as U(>). >n the basis of the empirical formula we might naively expect there to be a total of F&+'!/ " / normal modes of vibration associated with this material. 5owever this assumes that U(>) is covalent.

$ In fact U(>) consists of an ionic lattice of UN and (>)! ions arranged in an infinite and very regular array. The crystal consists of essentially isolated UN ions and (>)! ions. Thus we are able to consider the vibrational modes of the cation and anion independently of one another. In this case since the potassium ions are monatomic they have no vibrations &F&1'!F " 0' so we need only consider the nitrite anions. The 1:<@. &1alence :hell <lectron @air .epulsion' Theory predicts a bent structure for the nitrite ion. ;e thus anticipate three normal vibrational modes for (>)! corresponding to the diagrams drawn earlier for 5)> and they should all be infrared active.

$ Indeed three bands are observed in the I. spectrum of U(>)8 the symmetric stretch at 1FF* cm!1 the asymmetric stretch at 1)*0 cm!1 and the bending vibration at 8F0 cm!1 &bending vibrations occur in general at lower fre3uencies than stretching vibrations'. The fre3uencies of these vibrations are about the same regardless of counter ion substantiating the independence of the anion and cation in the crystal.

$ $

!4- aldehydes ?efore concluding the discussion of the carbon hydrogen bond one additional type of 7!5 stretch can be distinguished the 7!5 bond of an aldehyde. The 7!5 stretching fre3uency appears as a doublet at )7*0 and )8*0 cm!1. <xamples of spectra that contain a 7!5 stretch of an aldehyde can be found in -igures 1+ and 1*. Dou may &should' 3uestion why the stretching of a single 7!5 bond in an aldehyde leads to the two bands 6ust described. The splitting of 7!5 stretching fre3uency into a doublet in aldehydes is due to the phenomema we called "-ermi .esonance". It is believed that the aldehyde 7!5 stretch is in -ermi resonance with the first overtone of the 7!5 bending motion of the aldehyde. The normal fre3uency of the 7!5 bending motion of an aldehyde is at 1FG0 cm!1. 2s a result of this interaction one energy level drops to ca. )7*0 and the other increases to ca. )8*0 cm!1. >nly one 7!5 stretch is observed for aldehydes that have the 7!5 bending motion of an aldehyde significantly shifted from 1FG0 cm!1.

$ (rimary amines and amides derived from ammonia The (!5 stretching fre3uency in primary amines and in amides derived from ammonia have the same local symmetry as observed in 75). Two bands a symmetric and an asymmetric stretch are observed. It is not possible to assign the symmetric and asymmetric stretches by inspection but their presence at approximately FF00 and FF+0 cm!1 are suggestive of a primary amine or amide. These bands are generally broad and a third pea9 at fre3uencies lower than FF00 cm!1 presumably due to hydrogen bonding is also observed. This is illustrated by the spectra in -igures 18 and 1G for n!butyl amine and ben4amide.

$ Esters5 aldehydes5 and 6etones $ <sters aldehydes and 9etones are fre3uently encountered examples of molecules exhibiting a 7"> stretching fre3uency. The fre3uencies 17F* 17)* 171* cm!1 respectively are too close to allow a clear distinction between them. 5owever aldehydes can be distinguished by examining both the presence of the 7!5 of an aldehyde &)7*0 )8*0 cm!1' and the presence of a carbonyl group. <xamples of an aliphatic aldehyde ester and 9etone are given in -igures 1+ F+ F/ and F* respectively.

$ #itro group $ The final functional group we will include in this discussion is the nitro group. In addition to being an important functional group in organic chemistry it will also begin our discussion of the importance of using resonance to predict effects in infrared spectroscopy. =et[s begin by drawing a Ue9ule or =ewis structure for the nitro group. Dou will find that no matter what you do it will be necessary to involve all * valence