we get the Sipratton-roTationspectrum of the molecule. These spectra are in the near infrare YeBiOW, —— : If transitions occur between different electronic-vibrational-rotational energy ‘levels, we get the of the molecule. These spectra are in the visible and ultfaviolet region: = 19.7. Theory of the origin of pure rotational spectrum of a molecule : We may picture a diatomic molecule as consisting of atoms of masses m, and mp a distance R apart. liatomic molecule can rotate about its ‘centre Axis of mass Centre of The moment of inertia of this molecule abeut att axis passing through and perpendicular to a line joining the atoms is P= mrt my a) where r; and rp are the distances of m, and mz, respectively from the centre of mass. From the definition of centre of mass its centre of m: 470 . Moder Physics are in the microwave and far infrared regions If the molecule remains in its ground state level of electronic energy, and if transitions occur between different vibrational and rotational energies t i myry = mary (2) Further R=ntn 1G) From equations (2) and (3) m; mi n= SR and 2 = 1 | my + my my +m i Putting these values of r, and r2 in Eq. (1), p= minha, mga Ma pp (m+ my (im + mY (mm +m) or . r= \R wf)i } i | { Lasers. Molecular Spectra and Raman Effect wes F nv. the photographic Reference beam ca plate at A, B and Se €, but the relative. —___»_— phases of the 7 scattered beams are such as to give 0, -1, and +1 at A, B and C, respectively. Then, if the light is coherent, we must add amplitudes, before squaring to give the inten- plate sity. This gives resultant inten- Fig 198 sities of 1, 0 and 4 at A, B and C, But in the absence of the reference beam the intensities would be 0, 1, and 1, We have therefore recorded on the photographic plate the information that the phase of the scattered light at differs from that at C. Clearly, for this process to work, the light must be coherent over a reasonable area. If the photographic plate is developed and illaminated with a coherent beam similar to that used as a reference, an ob- server sees a complete, three-dimensional reconstruction of the Object. As he moves his head, the perspective of the image changes in exactly the same way as that of the object. MOLECULAR SPECTRA 19.6. Introduction : Apart from the ground state, a molecule can be in a higher energy state, and transitions between the various energy levels give rise to the observed molecular spectra. The energy of a diatomic molecule arises from three modes : i. the electronic configuration of the electrons in the molecule, ii, the vibration of the atoms about the equilibrium position, and iii, the rotation of the molecule as a whole about its centre of mass. The total energy of a molecule can be expressed as the sum of three independent terms : Mirror ~~ Object Photographic E=E,+E,+E, ) E,, Ey E,are quantised and = E, > E,, If the molecule remains in its groand state TeveT Of electronic and vibrational energies, and if it suffers transitions between different rotational energies, we get the pure rotational spectrum of the molecule:\These spectramioaem Fnysics Importance of the pure rotational spectrum for determining the proper- ties of a molecule : The frequency difference between two Successive lines in the pure rotational spectrum of a diatomic molecule is given by # AYE Yt ay re = By measuring”A ¥, the moment of inertia of the molecule can be calcu- lated. Now, 7 my my 2 Tam R= {Mim | 2 fee +m) } Thus the distance R between the nuclei can be calculated. This gives the length of the chemical bond between the atoms. Example : In the CO molecule the wavenumber difference between the successive absorption lines in the pure rotational spectrum ts 384 m-! Caleulate the moment of inertia of the molecule 4nd the equilibrium bond length of the molecule. Masses of the C!? and O atoms are respectively 1.99. 10° ke and 2.66 x 10° ke. Here, a = 5% = 3gayr! a 1.054 x 10° ——1.054 x 107 — = = 1456 x 10° kg m? 2nchY In x Bx 10) x 384 x % The reduced mass un’ of the CO molecule is yim _ [1.99 x 2.66 26 po 1-26 a = TEES Da 10% bg = 1138 3 10 bg + Bondlengu = x = VI _ 1456 10 = 0.1131 nm m 1.138 x 10 19.8. Theory of the origin of the vibration-rotation spectrum of a molecule. When sufficiently excited, a molecule can vibrate as well as rotate. We shall consider only diatomic molecules. Fig. 19.11 shows how the ential ¢ iatomic mol the internuclear distance —&.In the neighbourhood of the minimum of this curve, which Corresponds to the normal configuration of the molecule, the shape of the curve is very nearly a parabola. In this region, then V= Vor+ Rk (R= Ry? -() where R, is the equilibrium separation of the atoms, The interatomic force that gives rise to this potential energy F =-dVidR = -&(R-R,) (2) The force is just the restoring force that a stretched or compressedsepececetone semen Lasers, MUIcCUIa! oper where the reduced mass’ is defined as -_ mm m +m GQ) ‘The angular momentum L of the molecule has the magnitude L = 10. ‘The angular momentum of the rotating diatomic molecule is quantised ac- cording to 6) J is called the rotational quantum number. 1 The rotational kinetic energy of a diatomic molecule is 570° 2 ) S E, = 410 = 5 = tush mt, > Rotational transitions occur only in those molecules which possess a per- manent electric dipole moment. For this reason nonpolar diatomic molecules such as Hy and symmetric. polyatomic molecules such as CO, and CH, do not exhibit rotational spectre. ~~~ ~ 0 +1 (8) ‘The selection rule for rotational wansitions is AF = Rotauonal spectra are always obtained in absorption. Hence for a transition from some initial state of quantum: number J to the next higher state of quan- tum number J + , the frequency of the absorbed photon is BE Eyer ~ Ey -futp O Visas =F h “The spectrum of a rigid molecule therefore consists of equally spaced lines le (Fig. 19.10). eq ———z— potaional ets” aa 681 Rotational Moeewum) | 9 Fig. 19.10E,= (» +4) avy -(5) Here v is the vibrational quantum number. It may have the values vy = 0,1, 2, 3,... Substituting the value of v, from Eq. (4), B= (v+hyaye- (6) a These levels are sketched on Fig. 19.13, Fig. 19.13 For large-amplitude vibrations, the parabola does not fit the actual energy curve. Eq. (6) no longer holds. The energy well is wider than the Parabola for the higher E,’s, and therefore these energy levels are closer together than the lower £,’s, This di also shows. ine si re in the vibrational lev by the simultaneous excitation ional levels> ‘The selection rule for transitions between vibrational states is Av=tl (7) CPure vibrational spectra are observed only in liquids. This is because interactions between neighbouring molecules prevent their rotational mo- tion. JLasers, Motccurar oper v R /_ Paravotic approximation Vo Fig. 19.11 spring exerts and, as with a spring, @ molecule suitably excited can undergo lations, Classically, the frequency of a vibrating body simple harmonic oscil air mwass m connected to a spring of force constant kis a Yo = 26 vE GB) ave two bodies of masses m, and m> joined by dd mags” reduces the problem of two particles of mass to the problem of a In the diatomic molecule we hi pang. The use of the “reduces m, and m; vibrating about their common centre single mass m' vibrating about fixed point (Fig. 19.12). The frequency of oscillation of such a two-body oscillator is 4 ™ @VOUVNVDOD0O0 mam STITT When the harmonic oscillator problem is solved quantum mechanical- ly, the energy of the oscillator is found to be restricted to the values(i) P Branch : Here, AJ= -1 (.e.,J > J-1). From Eq. (8) the frequencies of the spectral lines in the P branch are given by Exs-1~ Foy _ 1 [KR py. w i =< wp tlw ys-su+y ) ro or y= % Po F = 1,2,3,... (9) (ii) R Branch: Here, AJ = +1 (ie, J J+ 1) g+1~ Fos _ 1 [k a v= i = on He t Wengen —sorn | ge or p= yt Ut) 4 J=0,1,2, 3, oun (10) ‘There is no line at = vo (the Q branch) because transitions for which AJ = 0 are forbidden in diatomic molecules. (ihe spacing between the lines in both the P ard the R branch is as 4 Hence, by measuring the frequencies of these lines, the moment | of inertia of the molecule and the length of the chemical bond can be calcu- ‘ al vibration - rotation molecular spectrum of It is made by sending radiation from a source of continuous infrared wavelengths through a cell containing HBr and recording the absorption spectra. § 100 2 oo / § 80 { “of t & 2 é i 2700 2600 2500 2400 <— Viem) Fig. 19.15 19.9. Electronic spectra of molecules : When there is enough available energy, the electronic states of the molecules can be excited. This gives rise to the most general type of transitions, rotation-vibration-electronic transi- tions, These produce photons of frequency Ee, ~ Bey | Evy - Evy | Ewa = Fron 7 n° Oh iLasers, Molecular Spectra ana Kaman EITeCt 41> ‘The vibrations and rotations of a molecule take place independently of each other. Under these circumstances the energy levels of a diatomic molecule are specified by | Bast mE say ® 8) . I 3 E, is very much larger than E,. Even at high temperatures only the vibration- al states corresponding to v = 0 and v = 1 are excited. Fig: 19.14 shows the J =0, 1, 2,3 and 4 levels of g diatomic molecule for the v = 0 and v = 1 vibra- p—————; J=4 3 ; 1 ye2f = at J =) 7 J=0 Energy P branch R branch Fig. 19.14 tional states. It also shows the spectral lines in absorption. The selection rules are Av = 1 and AJ = + 1. The transition with A/ = 0 is not allowed. The » = 0 > v = 1 wansitions fall into two categories :478 Modern Fhysics this reason, Raman effect is also called incoherent scattering antl is con- sidered as the optical analogue of the Compton effect. 19.12. Experithental study of Raman effect : The apparatus shown in Fig, 19.16 first developed by Wood, is used for studying Raman effect in liquids. It consists of a glass tube AB containing the pure experimental liquid free from dust and air bubbles. The tube is closed at one end by an optically plane glass plate W and at the other end it is drawn into a horn (H) and blackened on the outside. Light from a mercury arc § is passed through a filter F which allows only monochromatic radiation of A = 4358 A to pass through it. The tube is Spectrograph Fig. 19.16. surrounded by a water-jacket (J) through which water is circulated to prevent overheating of the liquid. A semi-cylindrical aluminium reflector R is used to increase the intensity of illumination, The scattered light coming out of W is condensed on the slit of a spectrograph. The spectrograph must have a large light gathering power and the prism must'have a large resolving power. A short focus camera is used to photograph the spectrum. On developing the photographic plate, it exhibits a number of Stokes’ lines, a few anti-Stokes lines and Original tine | 4358 & a strong unmodified line (Fig. _ 19-17). ‘Antistokes’ line | Stokes" line Characteristics of Raman Lines : (1) The Stokes lines are always more intense than antistokes lines. (2) The Raman lines are symmetrically displaced about the parent line. (3) The frequency difference between the modified and parent line represents the frequency of the corresponding infrared absorption line. 19.13. Quantum Theory of Raman Effect : Raman effect is due to the in- teraction between a light photon and a molecule of the scatterer. Suppose a Fig. 19.17 |so Lasers, Molecular Spectra and Raman Effect AaqT Itis the outermost electrons of the atoms composing the molecules that are involved, These transitions are energetic enough that they produce electronic bands in the visible and ultraviolet regions. All molecules exhibit electronic spectra, since a dipole moment change always accompanies a change in the electronic configuration of a molecule. In molecular spectra, as in atomic spectra, radiative transitions between electronic states of dif- ferent total spin are forbidden. 19.10. Rayleigh’s Scattering: Rayleigh showed theoretically that the inten- sity of scattered light is inversely proportional to the fourth power of the wavelength Le. ,. This is known as Rayleigh’s law of scattering. / is also proportional.to the square of the volume of the particle. The blue colour of the sky is due to the greater scattering of short wavelengths by the dust suspensions in the atmosphere or by the air molecules. This type of scatter- ing simply produces separation of wavelengths originally present in the in- cident light. No wavelength can be present in the scattered light which is not present in the incident light i.e., no new wavelength is created. For this reason, Rayleigh scattering is called coherent scattering. RAMAN EFFECT 19.11. Discovery : While studying the scattering of light, Raman found that when a beam of monochromatic light was passed through organic liquids such as benzene, toluene, etc., the scattered light contained other frequencies in addition to that of the incident light. This is known as Raman effect. The original arrangement used by Raman was simple in design. A round-bottomed glass flask was filled with pure dust-free benzene. The liq- uid-was strongly illuminated by the mercury blue line of wavelength 4358 A. The scattered light was examined through a spectroscope in a direction perpendicular to that of the incident beam. It was observed that the spectrum contained, in addition to the original wavelength (4358 A), some lines which had wavelengths longer as well as shorter than the original wayelength. These lines of modified wavelengths are known as Raman lines. The lines having wavelengths greater than that of the incident wavelength are called Stokes lines and those having shorter wavelengths are called anti-Stokes lines. The Stokes lines are found to be more intense than the anti-Stokes lines. Most of the Raman lines are strongly polarise The displacement of the modified spectral lines from the exciting line, when measured in wavenumbers, depends only on he scattering subsancs and is independent of the wavenumber of the exciting radiation. The Raman spectrum is thus characteristic of the scattering substance.\Raman effect is quite different from Rayleigh scattering. In Rayleigh or coherent scattering, there is no change in wavelength. But in Raman scattering, the scattered light contains modified wavelengths as well as the original wavelengths.\Foroo Modem Fnysics Raman Spectra Fluorescence Spectra 1, Spectral lines have frequen- The frequencies of the lines in cies greater and lesser than the fluorescent spectrum are al- the incident frequency. ways less than the incident fre- quency. 2. The frequency shifts of the Frequencies of the flourescent Raman lines are determined lines are determined by the na- by the scatterer rather than ture of the scatterer. the frequencies themselves. 3. Raman lines are strongly polarised. Lines are not polarised. 19.14. Applications. (1) Raman Effect and Molecular Structure : A qualitative iden- tification of Raman spectrum consists in the evaluation of the wavelength of the lines, their intensities, and state of polarisation. Investigation of bond angles, bond stiffness, and other structural confirmation require Raman data in addition to infrared studies. _ (i) Diatomic Molecules : From the analysis of Raman spectra of a diatomic molecule, we can have an idea about the nature of the chemical bond existing between the atoms. In a diamotic molecule, the frequency of 1 on force per unit displacement and 1 is the reduced mass-of the molecule. It is seen that a molecule in which-the force binding the atoms is great should have higher characteristic frequency than one in which the force is weak. This force depends upon the nature of interatomic bonds, In covalent molecules polarisability is considerably changed by the nuclear oscillations due to the nuclei. This appreciable change in polarisability gives rise to in- tense Raman lines. In clectrovalent molecules, the binding electrons definitely change over from one nucleus to the other in the formation of the molecule so that the polarisability of the molecule is litle affected by nuclear oscillations and hence no Raman lines will appear. (ii) Triatomic molecules : Dealing with triatomic molecules (of type AB,), the questions to be decided are : whether each molecule is linear of not and, if linear, whether it is symmetrical (B - A - B) or asymmetrical (B - B - A). From the number and intensity of the observed lines in the Raman effect in conjunction with infra-red data, it is possible to draw important con- clusions about molecular structure. Theory leads to the following rule, known as the.rule of mutual exclusion. It states that for molecules with a centre of symmetry transitions that are allowed in the infra-red are forbid- den in Raman spectra and vice versd. The rule does not imply that all transi- vibration-of the atoms is given by ¥ = aaa where F is the restoringLasers, Molecular Spectra and Raman Effect 479 photon of frequency »; is incident on a molecule and there is a collision be- tween the two. Let m = mass of the molecule, v; and v2 its velocities before and after impact, E, and E> the intrinsic energies of the molecule before and ‘after collision. Let v9 be the frequency of the scattered photon. Applying the principle of conservation of energy, Ey + Jaw} + hy, = Ey + dwt + hy (1) We may assume that the K.E. of the molecule is unaltered during the process. Hence, - Ey Eq + fv, = Ey + hy, Ory E, - Ep or 2) Three cases may ari hen there is no change in the energy of the molecule, Ey = Ey. {hen vy v2. This represents the unmodified line If E, > E,, then, v2 < ¥,. This represents the Stokes line. It means that the molecule has absorbed some energy from the incident photon. Con- sequently the scattered photon has lower energy or longer wavelength. If Ey < Ey, then, 7) > ¥;. This represents the antiStokes line. It t the molecule was previously in the excited state and it handed me_of its intrinsic hoton. The scattered photon thus has greater energy or shorter wavelength. Since the molecules possess quantised energy levels, we can write, E, ~ Ey = nhy, 8) where n = 1, 2, 3-clc., and ¥, = the characteristic frequency.of the molecule, In the simplest case n = 1, equation (2) reduces to vty, (4) Y2 Equation (4) shows that the frequency difference v, ~ v2 between the incident and scattered photon corresponds to the characteristic frequency V. of the molecule. * aman Effect and Fluorescence ; Raman ettect and fluorescence resemble each other in that the incident light in both the cases suffers a change of wavelength and lines of new wavelengths appear in the spectrum of either, But the Raman effect is quite different from fluorescence. We compare the two phenomena in the table.Lasers, Molecular Spectra and Raman Effect 481 tions forbidden in one must occur in the other ; i.e., some transitions may be forbidden in both. On the other hand certain transitions can occur both in the infra-red and in the Raman spectra in the case of molecules without a centre of symmetry. Examples : (a) CO2 has two very strong bands in its infrared absorption spectrum at 66800 and 234900 m” while only one strong band in its Raman spectrum at 138900 m-', None of these bands occur both in Raman and infrared spectra. Hence, it follows from the rule of mutual ex- clusion, that CO molecule has a centre of symmetry. This implies that the molecule is linear and symmetric and hence it should be represented by 0-C-0. (b) Nitrous oxide (N20) has three absorption bands at 222400, 128500 and 58900 m” of which the first two appear in the Raman spectrum. Thus the molecule cannot have a centre of symmetry though linear. Hence the molecule has the unsymmetrical structure N - N - O. Ina similar manner, the bent symmetric structure of a water molecule represented by Fig. 19.18 is revealed by Raman Effect. Thus the study of Raman spectra of different substances enables one to classify them according to their molecular structure. ag, 19.18 (2) Raman effect in crystals is complimentary to X-ray crystal study and provides intormation about the binding forces in crystals. (3) Various chemical effects like strength of chemical bonds, electrolytic dissociation, hydrolysis etc, have been understood through Raman effect. Specific heat capacities of solids, brilliance of metals and their molecular structure have been explained by Raman effect. EXERCISE 19 Describe the principle, construction and v a ruby laser. Describe the working of the helium-neon > '#ser. Describe the general features of molecular spectra. aes Give the elementary theory of the origin of pure rotational spectrum of @ molecule. 5. Give an elementary theory of the origin of the vibration-rotation spectrum of a molecule. 6. The CO molecule has a bond length R of 0.113 nm and the masses of the c? and O'° atoms are respectively 1.99 x 10°” kg and 2.66 x 107° kg; Find the energy and angular velocity of the CO molecule when it is in its lowest rotational state. (Ans. 4.756 x 10% eV; 3.23 x 10“! rad/s). 7. The force constant k of the bond in CO is 187 Nm. Find the frequency of vibration of the CO molecule and the spacing between its vibrational energy levels, (Ans. 2.04 x 10!? Hz, 8.44 107 eV). 8. Give the theory of Raman effect and “escribe an experimental arrangement for studying it,