Rotation of Molecules 169 WORKED EXAMPLES fhat is the change in the rotational constant 8 when hydrogen is replaced by deuterium in the hydrogen molecule? Denoting the isotopically substituted hydrogen by primes Bolivia POT gp | e mp | aa = =H | BL 2my _ Be my =2, ‘Change in rotational constant, B — B’ = B/2. fe first line in the rotation spectrum of carbonmonoxide has a frequency of 24cm". Calculate the rotational constant and hence the C-O bond length in carbon monoxide. Avogadro number is 6.022 x 10”/mol + aw 2B = 38424 cm", B= 19212 em! = 192.12m' a he t= pes 4 ie ~ eae’ Br uBe (12g/mol) (15.9949 g/mol) = ON = 11385 x 10° # * 7.9949 g/mol) (6022 x 10 /nol) 5 6.626 x 10-1, 8x? (1.1385 x 10-*kg) (192.12 m) (3x 108 m/s) r= L131 x 107m = LISA. yhat is the average period of rotation of HCI molecule if it is in the J = 1 state. The internuclear distance of HCI is 0.1274nm. Given the mass of hydrogen and Chlorine atoms are 1.673 x 1077 kg and 58.06 x 107” kg respectively. 1 Rotational energy of a classical rotator = gla 2 Rotational energy of a quantum rotator = gy +1) 1 7 WI +) Equating the two, a = ——S7— quating aaa 2_ (1673x1077 kg) (58.06 x10" kg) (0.1274 x 107° m)? 7 59.733x 10°" kg. = 0.0264 x 107 kg m? T=pr170 Molecular Structure and Spectroscopy = PVIUFD _ _(6626x10-* 1.8) [2 = 56.5116 x 10!"s* 2a 2m (0.0264 x 10-“kgm?) Period of rotation 7 = 2% = aa = ee = 2 x 10°’ @ ~ 565116x 10"s © i first rotational line of '°C'0 is observed at 3.84235 cm and that of '°C!%0 at .67337 em", Calculate the atomic weight of “IC, assuming the mass of '%0 to be 15.9949. Writing B for the rotational constant of "C!0 and BY for that of ?C!%0 Bote BOT a Let the atomic weight of °C be m. H _ _27.9949 x IX 159949 H ~ 12x 159949 ™ (m+ 159949) B _ 3.84235 em! & = em = 1.046 B’ 3.67337 em" = 279949 _m_159949 1.046 = 75159949 * (m 159949) Simplifying 13.001 Atomic weight of "°C is 13.001. 6.5 Rotational and centrifugal distortion constants of HCI molecule are 10.593 cm” and 5.3 x 10cm! respectively. Estimate: the vibrational frequency and force constant of the molecule. 4B° Centrifugal distortion constant D = - [oe Force constant k = 427 uv? -2 27 ae ee kg) _ 1.6261 x 1077" kg 4n2 x (3 x 108 m/s)*(1.6261 x 10°?” kg)(2995.2 x 10? m4? ays scone) = 2995.2cmr! = 2995.2 x 10%m™ = 517.8Nm! 6.6 Three consecutive lines in the rotational spectrum of a diatomic molecule ‘are observed at 84.544, 101.355 and 118,112 em’, Assign these lines to their appropriate J” —> J’1: > Rotation of Molecules. 171 deduce values of B and D. Hence evaluate the approximate vibrational ‘\ tansitions and frequency of the molecule. Frequency of J > J + | transition 2B +1) - 4D +P s 84.544 em! = 2B V+ 1)-4D V+ IP 101.355 em"! = 2B U + 2)- 4D J + 2? | 18.112¢m"! = 2B U +3) - 4D J + 3) | From the first two equations 16811 em! = 2B - 4D (U + 2° - + 1) Since D << B, an approximate value of B can be obtained by neglecting the term in D. With 2B = 16.811 cm, again neglecting the term in D 84.544 cm! = 16.811cm! (J + 1) J = 4.03 = 4 (corrected to the integer) Therefore, the line at 84.544 em" correspond to J = 4 -» J = 5 transition, the one at 101.355 cm’! is due to J = 5 - J = 6 and the one at 118.112cm"! is due to J=6— J = 7. With these values 84.544 cm”! = 2B x 5 ~ 4D x 125 101.355 em"! = 2B x 6 - 4D x 216 Solving, B = 8.473 cm™!, D = 3.7 x 10cm"! 4B D= e 4(8473cm™')> > 2564.4 em™! 3.7% 10-* em observed rotational spectrum of HF shows the J = 0 + J = 1 absorption at I.J1cm’', the spacing between adjacent absorptions is 40.08 cm around = 5 + J = 6 transition and only 37.81cm around J = 10 > J = 11 transition. Calculate B values and J values from these three given data. What explanation can you give for this variation. —— Around J=O—>J=1, 2B= 411m, = 20.56 cm" Around J=5 > J=6, 2B = 40.08cem, B= 2004cm™ Around J= 10 > J = Il, 2B= 37.81cm', B= 1891 cm = . © Bre = > 6626x1088 = 369 x 10 ke mm? - *! gives | = ————--_—* 2056 m-" gives 8x? x 2056m"! (3x 10" mV/s)ay Strwcture and Sjec troscopy Bs 2004! gives 7 WW Bives Fe L071 x 19 "Khe om Res Fe Last x 19 he m? distortion, the eXptession for the Bs 1890t ay! Including centritugat frequency of a transi Vis 280 41) apy + ay As the term 4D 4 1)! decreases as J incre Vibration of the atoms ate i 'S always positive, the separation between energy levels m other words, in the excited states the amplitude of pected (0 be larger which increases the moment of inertia f -1 © ocotationall constant for H®CHN and DCN ate 1.4782 and. 1.2077 em ively, Calculate the Moments of inertia of these molecules and intemuclear distances of C—H and Cm N bonds MAL of HON 1 = = 1.804 x 10 kgm? 6.626 10° Js 8x? x 120.77m™" (3x 10% m/s) 7 2 MLL of DCN as in = — = 2.3182 x 10% kg m From Eqs. (6.23) and 6.24), we get 2 re mietey + memyrey + myMy (Te Ten) my me My 2 Momerey + menyrey + mpmy (ren row)! mp Mig my where — L008 Ux 107 kg, my = —2014 9 = 3.344 x 1027 k m= Sona x1o® MEH 12t x B > = Son x10 i = capa Ke = 19.927 x 107" kg, my = 14003 kp = 93.953 x 10°27 Me Soa Tow ME= PTX ION KB mm = SO oe he s Substituting the values of the masses and moments of inertia 1 and I 848.53 x 10° kg m? = 32.302 Poy + 463.363 Pay + 37.693 (rou + ren)® 1078.52 x 10 kg m? = 66.636 rq) + 463.363 Poy + 77.59 (roy + Ton)? On simplification, ton = LOTA, rey = 116A ion for the frequencies of the Stark components of the J linear molecule, 6.9 Derive expt transitions of The first order correction to a linear molecule is zero and the second order correction is given by Eq. (6.43). For the J = 1 and 2 statesRotation of Molecules 73 ay2 2y2 2 x 902) Lex ER e LHX Ee L n= 10 Bh ES 20 Bh ay? ay? pe). Lex ni) _ L wex 205 9 A Ba Bh Selection rules AJ = tl and Am, = 0 allow two lines. Their frequencies are: £% 8 ex? Vimy = 0) = Vy SE = Wy Gg ae eR iy wx? =e E y+ A oA vim = = y+ pt ee Here Vp is the rigid rotor frequency of the zero field line. The coefficient of X° in the ions are sometimes referred (0 as Stark coefficients. second term of the above equa (0 Astimate the minimum kinetic energy at which a neutron, in a collision with a molecule of gaseous oxygen, can lose energy by exciting molecular rotation. The bond length of the oxygen molecule is 1.2 A. we a D a7 IU * 1 joules, Y= 0, 1, 2, The rotational energy levels are Ey To excite molecular rotation, minimum of the energy that must be absorbed by the E, " B 1 = u +I g u ur (16kg/k.mol)(16kg/k.mol) y= CORB mee NE = 1.329 x 107k, bs (32 kg/k. mol) (6.02 x 10°5/k. mol) e Mg? (1.05% 107" 18)__ = 0.5761 x 10775 Enin = oy ede ” (1329 x 10 kg) (1.2 x 107" my? 2 = O5761K10 IT .36 x 10 ev 16x10" H/eV The minimum K.E the neutron must possess is 3.6 x 10*eV. REVIEW QUESTIONS 1. Distinguish between symmetric top (prolate and oblate), spherical top and asymmetric top molecules. 2. To which symmetric top, the benzene (C,H,) molecule belong? 3. Dintomic molecules such as CO, HF will show a rotational spectrum whereas Np, 0}, Hy... will not. Why? Will the molecule 0 - 80 show a rotational spectrum? 4, The intensity of J = 0 -> J = 1 is offen not the most intense rotational line. Why?174 Molecular Structure and Spectroscopy 5. What is centri al distortion? Explain the effect of centrifugal distortion on the moment of inertia and energy of a diatomic molecule. 6- How knowledge of centrifugal distortion constant helps one to determine the force constant of a bond? 7. Outline the effect of isotopic substitution on the rotational spectra of molecules. 8. The observed rotational Spectrum of HF shows decrease in the line separation on the high frequency side. Why? 9. What is Stark effect? Outline the importance of Stark effect studies in microwave spectroscopy? 10. What is nuclear quadrupole moment? How does it differ from nuclear quadrupole coupling constant’? 11. Explain the construction details of Stark cell of microwave Stark modulation spectrograph 12. Outline the importance of the study of quadrupole hyperfine interaction in microwave spectra, 13. Explain the difference between equilibrium internuclear distance r, and internuclear distance ro, PROBLEMS 1. The bond length of HF molecule is 0.0927 nm (a) What is its moment of inertia ? (b) What is the value of rotational constant in joules and in cm”? (c) Find the wavenumbers of the first four-transitions. (d) Mention the spectral region in which these absorptions occur. 2. The average spacing between successive rotational lines of carbon monoxide molecule is 3.8626 cm'. Determine the transition which gives the most intense spectral line at temperature 300K. 3. How many revolutions per second does a CO molecule make when J = 3? The CO bond length is 0.1131 nm. 4. How many revolutions per second does a CO molecule make when J = 4? The Rotational constant of CO molecule is 1.9313 cm™!, 5. The microwave spectrum of CN radical shows a series of lines spaced by a nearly constant amount of 3.798 cm". What is the bond length of CN? 6. The separation between lines in the rotational spectrum of HCI molecule was found to be 20.92cm"', Calculate the bond length. 7. The rotational constant for HCI is found to be 10.5909 em”, What is de value of B for HC} and for D°SCl 7 Given that m(*Cl) = 35.45 g/mol, mC"Cl/m@Sch = 1.056. . 8. Show that a substantial number of molecules of a gas are in excited rotational states at temperature 300K. 5 9. The first Tine in the rotational spectrum of carbon monoxide has a frequency of 3.8424 cm”!, Calculate (i) the moment of inertia of the molecule. (ji) its angular. In HCI a number of absorption fines with wave nu Rotation of Molecules 175 momentum and angular velocity in the J = 3 state. (iii) the wave number of the transition J = 5 + J = 6. imbers 83.03, 103.73, 124.3, 145.03, 165.51 and 185.86¢m"' have been observed. Are these vibrational or rotational y? If they are transitions? If they are vibrational, what is the characteristic frequenc; rotational, give the J’ values of the 83.03 cm”! transition and the moment of inertia of HCI. In that case estimate the internuclear distance.