MICROWAVE AND Ip SPECTROSCOpy 10.1 MICROWAVE SPECTROSCOPY 10.1.1 Bond Length and Reduced Mass ‘Atoms in a diatomic molecule are held together by a chemical bond and undergo rotation and vibration through absorption of electromagnetic radiation in IR range. However, these rotational and vibrational energies are much smaller than bond breaking energy. Rotational energy usually lies within 10-100 J/mole while vibrational energy usually lies within 10 kJ/mole. Spectroscopy in microwave region is concerned with the study of rotating molecules, which are considered as rigid rotors. Rigid rotor: The molecule, in which bond does not distort during rotation of molecule about the bond axis, is called rigid rotor, shown in the Fig. 10.1. Furthermore, in case of rigid rotor system, molecules are rotating without any vibration. -— fe Angular motion Figure 10.1 Linear motion and angular motion of molecule in a rigid rotor system. Ina diatomic molecule the atoms are rotatit igi i its _ ting as a rigid yect to its centre of gravity (CG) as shown in the Fig. 102. iMicrowave and IR Spectroscopy 305 > 71, Figure 10.2 Rotation of a diatomic molecule, CGis operating at the point C. Bond length = Atequilibrium, we have eae ‘The moment of inertia is given by itn = mar? + migry = myrgy + mph = HPC +) Mf = mar —))- Again, mgr, = my" myry = marry). OF, MyM mg) = me | Or, | | Similarly, Hence, (10.1) 1 T= wand p=—+> wand w= 7 Where, 11 is called reduced mass. . Rotation of.a diatomic molecule is equivalent to rotation of "fom the origin C. ‘mass pata distance 101.2 Rotational Energy Rotational ki Te = Angul tu wal Kinetic energy is given by >, where, J= UO ane area {thas been established that ? = Square of the magnitude of angular momentum = JI Wh >306 Chemistry for Engineers Thus rotational energy, E, is given by 2 v ki * y(s4)= Ss (J +1)= BI (J 4), 7 a ( ) 8x°I ( ) ( ) Pow where, wer or E,=BUJ+ 1) (10.2) Case 1: Energy difference between two successive energy levels, J and (J+ 1) is given by ia AE = —-2(J +1)=2B(J +1). ai (J+1)=2B(J +1). he) = Again, AE = hv = kev Hence, Z 2v+n)-2pv+n]=5[2(+), cae 8r7Ic he B where, ie Poo 8n27 2T Or, v= BIV+1)) (10.3) Case 2: Energy difference between two successive energy levels, (J— 1) and Jis given by We Neha AE = ——(2/) = 2B. in, AE= hv= 2 = hev Pe) 7( ) Again, AE= v= Hence, h 2BJ on a7 |2J = — = 2B, (ea) he > "where, Or, v=2Bs 10.1.3 Population of Energy Levels Population at any energy level is governed by: (a) Boltzmann distribution function and (b) degeneracy of energy levels.Microwave and IR Spectroscopy 307 ide Boltzmann distribution function Es of molecules ay W 2 Number Peet Wailable at the ground state. Ny ze Number of molecules at any given energy state J. ign, is known, N, can be calculated using Bola grow g Boltzmann distribution function as Neen NS © -Eslhot = g- BIH hat _ Bul u+i)ie/kgr [Using equation (10.2)] -Bs(UH)he/ kt Or, (10.5) Thus, it is evident that population density decreases as J value increases. 10.132 Degeneracy of energy levels ‘The kinetic energy of rotational motion is given by 1, (ley _p? dig ak a2 = JET Zor ore Or, p= V2EI (10.6) p= Angular momentum = Jo, Again, E= F ju, Or, 261 = WP + 1) Putting the value of ‘E’ in equation (10.6), we get p= T(F+in= (I+) unit h = Fundamental angular momentum unit. eneracy is (2/ + 1). For a given value of J, the number of deg ible quantized states, -1, 0 and +1. Thus, for J = 1, there are three poss! p= V2= 1.14, 2, there are five possible quantized p= V6 =2.44, So, with the increase in JJ value, degeneracy increases and hence population also increases, eg ering the above two factors ( feneracy of energy levels) we can write states, -2, -1, 0, +1 and +2. Boltzmann distribution function and Population (27 +1) elke,308 Chemistry for Engineers Or, Ms (24 + 1)e"E/7 (10.7) : No ‘The population curve is shown in the Fig. 10.3. The diagram shows that population density initially increases with increase in J value, indicating that degeneracy factor is dominating over Boltzmann distribution factor. However, at higher J value Boltzmann distribution factor is dominating and hence population density decreases exponentially. Population — Figure 10.3 Population density versus energy level diagram According to the equation (10.7), we can write Ny = NoC(2J +1)e/7 | (where, Cis a constant) (10.8) At the maximum point of the above curve, we have Differentiating equation (10.8) with respect to J, we get my _ nge[zertinr (24-1) ty aT (10.9) Again from equation (10.2), we have BI(J+1)= BheJ (J +1) and = Bhe(2J +1) Putting this value of “4 in the equation (10.9), we get aN; _ NC aa: [2knT ~(2.) +1) Bhe(2.7-+1)]e-Fs/at At the maximum of the curve we have oe =0_ _______ Microwave and IR Spectroscopy 309 Using the condition of maximum, we have No Bi ne [2ker —Bhe(2J pag + ys 0. kT On Via t 1? = SP Hence, (10.10) 10.1.4 Selection Rules 1. Selection rule states that quantum number changes only by +1 or -1. Thus, for an allowed rotational transition, we have AJ = £1 and AM, = 0. All other transitions are spectroscopically forbidden. Probability of forbidden transitions is zero and probability of all allowed transitions is almost the same. 2. Selection rule also states that molecule, having permanent dipole moment only will show rotational spectra. So molecules, such as HCI, CO, etc. show rotational spectra but H,, Cl, will not show rotational spectra. 10.1.5 Characteristics of Microwave Spectroscopy 1. Klystron valve is the monochromatic source, which emits radiation over only a very narrow frequency range. 2. Electromagnetic radiation interacts with a molecule, changing to rotational state and the rotation gives rise to a spectrum. 3. Rotational transition occurs in the microwave region of the electromagnetic spectrum within 200 em~*. 4. Energy difference between two successive levels is given by Ey, ,-E,= AE = 2BU+ 1) and E)—E,_, = AE= 2B) 5. Bee 4. So the value of B decreases as J increases and hence the value of a AE decreases, Thus large molecules have closely spaced rotational energy levels, 6. Intensities of spectral lines increase with J and pass through a maximum. No = Total number of molecules, 8 = Degeneracy factor at the energy level J, N= Total number of molecules at the enerBy level J. Then, we can write that310 Chemistry for Engineers $$ aN, At the maximum point, J=Jyyae 2nd “y= 0. Hence, Jy, = 2 7. Rotational energy levels are degenerate and the number of degenerag is given by 2/+ 1. For J=0, there is only one degenerate level. For j=), there are three degenerate levels. 8, Energy difference between J = 0 level and J = J level is low. Rotation] population of /= I level is more than that of /= 0 level as the degeneracy of J=1 is 3 compared to J= 0, where degeneracy is 1. So, g)=3alJ=| level and g= 1 at/=0 level. 9. When molecules rotate with high speed, they cannot be treated as rigid rotors. There are distortions due to centrifugal force and other forces. Thus rotational energy expression needs modification and can be expressed as E,= BI(J+1)-DP (s+), 3 h where, D= Distortion constant = " <__ o—-oO Siretched bond Spring force —_—— o-O Compressed bond Figure 10.6 Vibrational stretching and compressing of a diatomic molecule-Microwave and IR Spectroscopy 313 o > Co (0) a L7 AN \ L/ t S a ie co oO ® {ny Syrnmetticstretel (b) Antissymmetsie stretch (e) Symmetric bend Figure 10.7 Stretching and bending processes of a triatomic molecule. Fach bond type can be excited ata characteristic frequency. When bond is excited to vibtate, it absorbs energy al a particular frequency, where a peak is observed. Stronger the bond, higher energy is required to vibrate. Vibrational excitation leads to stretching, compressing and bending of bonds. Vibrational transitions usually occur in IR range of electromagnetic spectrum. Classification of IR region is shown in the following table. Far IR ‘Mid IR Near IR | ktm) 3x 10403 x10 3105 to 3 x10 3x 10% to 7.8 x 10-7 vim!) | __3310330 330 to 3300 3300 to 12800 v(ilz) 1x 10! t0 1 x 108 1» 10 to 1 x10!4 1x10! to 3.8 * 10!4 Energy 0) | 66 ¥ 107? 10 66% 10-7 | 6.6 x10" 10 6.6 « 107 | 6.6 x 10° 10.6.6 « 10-7 The vibrational frequency range is 400 emr!-4000 cm”, Each functional troup has a characteristic IR frequency and hence structure of a molecule can be identified using IR spectra. Most of the funetional groups show bending vibrations within the frequency range 500 em-!—1500 em. This particular frequency range is called Fingerprint region. 10.2.2. Potential Energy Curves and Energy Levels Parabola Molecular potential enerzy Tntemnuclear separation Figure 10.8 Potential energy curves.314 Chemistry for Engineers Potential energy curve looks like a parabola and the expression of V’is given by Ye) = the? and.s= RR, (io. At R= R,, the curve shows a minimum, where, V'(x) = 0 and kis the force constant of the bond. Steeper the parabolic curve, stiffer the bond is and higher the value of k is. i Considering harmonic oscillator, potential energy, M(x) can be expanded using Taylor series as follows Y@)= VO OxtVO.8 + (10.12) ¥(0) = 0, according to the expression of M(x) and V'(0) = 0, at the minimum. ‘Neglecting the higher degree of x, we can write Vx) = av ).x” Hence, ke 370 (10.13) If V(x) changes sharply, kis large. If V(x) changes slowly, is small. energy, V — Potent x Figure 10.9 Change in k-value with steepness of the curve,Microwave and IR Spectroscopy 315 jnabarmonie oscillator, vibrational energy levels are shown inthe Fig, 10.10 Ss Potential energy 1/2(kx?) Internuclear separation, x X= 0 represents the equilibrium separation between the nuclei Figure 10.10 Vibrational energy levels in a molecule, whichis considered as harmonic oscillator. 10.2.3 Selection Rules 1, The molecule under investigation may not have permanent dipole moment but must gain temporary dipole moment during vibrational bending and stretching processes. Thus in general heteronuclear diatomic molecules are TR active but homonuclear diatomic molecules are IR inactive. Some heteronuclear diatomic molecules, like CO,, have no permanent dipole moment but they are IR active as they gain positive dipole moment during vibrational mode. 2. Transitions with Av==l, are all allowed transitions. When Av=+ 1, energy is absorbed and when Av = -1, energy is emitted, Other transitions, with Av=+2, 43, ..., ete. are forbidden transitions. 3. v=0 to v= 1 transition is normally called the fundamental vibration, while those with larger Av are called overtones. : 4. Av=0 transition is allowed between the lower and upper electronic states with energies E, and E, are involved, ie. (Ey, ¥ = 1) > (Ey ¥"= 1), where, and v" indicate the lower and upper quantum states respectively. 10.2.4 Characteristics of IR Spectroscopy 1. Permitted vibrational energy levels are given by 1 E,= (+5) myn and v=0, 1,2, my +m, where,316 Chemistry for Engineers (u), not on the total mass, E, depends on reduced mass Pie (T,) is given by E, is expressed in J and the term value tel 4] o ( 1) Fy ag) = 22 v4 = l=—l ts l=0,{y4! ee yea) (v4 «called harmonic vibrational constant with unit em”. v9 = a,¢ d zero point energy, which is trea y @, i i 2. The energy at v = 0 level is calle Fy= 5ho 3, Population ratio of the energy levels v= v, and v= v, is given by Si E-Bd/ ha nm Bi where, g, and g, are called degeneracy factors for the levels E, and g respectively. 4, Heteronuclear diatomic molecules are IR active and execute vibrational transitions. Homonuclear diatomic molecules are IR inactive and do not execute vibrational transitions. 5. Vibrational frequency is given by Ewa ~ Ey _ ho _ vk/u he he 2ne 6. The value of ¥ lies in IR region. Force constant value, k, can be calculated from vibrational spectrum data. Vibrational spectroscopy is observed within frequency range 400-4000 om 7. According to the selection rule, transitions with Av=+ | is called fundamental transition. The other transitions, Av = £2, £3, ..., etc. are called forbidden transitions with weak intensities. These transitions are known as overtones. 10.2.5 Applications of IR Spectroscopy 1, Calculation of relative positions of vibrational energy levels. 2. Identification of characteristic IR frequencies of different functional groups and hence molecular structure can be elucidated. 3. IR studies are widely used in pharmaceutical analysis. 4. IR study is useful to identify an unknown substance. It is used to establish whether a given sample of an organic substance is identical with another not. So if two compounds have identical IR spectra, both of them must be samples of the same substances. However, IR spectra of two enantiomers a compound are identical. So IR spe: : Me er wees enantiomers. ;pectroscopy fails to distinguish b*oe 5, IR spectroscopy is useful to study the reaction kinetics 6, IR spectroscopy is also effective to determine impurities. IR spectrum of the test sample to be determined is compared with the standard compound. Ifany additional peaks are observed in the IR spectrum, then it is due to impurities present in the compound. 7. IR spectroscopic method is used in quantitative analysis of a particular substance. The quantity of the substance can be determined either in pure form or as a mixture of two or more compounds. eee ss SS—— SS SOLVED PROBLE Given: B = 1.92118 cml. |. Calculate I and r of CO molecule.