“Microwave Spectroscopy It is concerned with transitions between rotational energy levels in the molecules, the molecule gives a rotational spectrum only If it has a permanent dipole moment: i) Ct Rotating molecule H-Cl, and C=O give rotational spectrum (microwave active). >H-H and CI-Cl don't give rotational spectrum (microwave inactive). Rotational spectroscopy is only really practical in the gas phase where the rotational motion is quantized. In solids or liquids the rotational motion is usually quenched due to collisions between their molecules. Which of the following molecules would show rotational spectrum: Br2 , HBr and CS2? Why?Rotational energy of a diatomc molecule Hera] oe ] eo t 8 Direction of dipole eae Sex Sra Vertical ‘component dipole The rotation of a diatomic molecule, HC\, showing the fluctuation in the dipole moment measured in a particular direction." General features of rotating system: 1- Rotational motion in classical mechanics Rigid Rotors: molecules in which bonds don't distort under the stress of rotation. Linear Motion Angular Motion ee Distance Re Linear velocity (v) = ---------- Angular velocity (w) = --- TimeLinear momentum (P) = m.v Angular momentum (J) =1. w Then; |=m.r, Where; the moment of inertia for a molecule (I) = ==m.r2 i i Where: ris the perpendicular distance of the atom i from the axis of rotation (bond length). Moment of inertia (I), also called mass moment of inertia which is a measure of an object's resistance to changes in its rotation rate. It is the rotational analog of mass.A molecule can have three different moments of inertia |,, 1, and |, according to the axis of rotation. [> Cl If In HCL, I, = 0, I,= le." Rigid rotors are classified into four groups: 1- Linear rotors: such as diatomic or linear molecules, as H-Cl, O=C=S, acetylene and O=C=0, have; I,=0 and I,= |,. 2- Spherical tops rotors: e.g. CH,, SiH, @ * and SF, have three equals moment of inertia.. la= Ib= Ic. 3- Symmetric tops rotors: e.g. Bes NH, CH,CN and CH,Cl, have two equal moments of inertia. , =I, # |. 4- Asymmetric tops rotors: e.g. H,0, I CH,OH, vinyl chloride CH=CHCI and, be formaldehyde, have three different Q= moments of inertia. 1, # |, # |.“ Classes of Rotating Molecules = Molecules can be classified on their moments of ine! into five main groups depending 1 = Ip, 1,70 Linear molecules 2. [=h=h Spherical top 3. |Ic=Ig> 1 Symmetric top I> Ip>I, Asymmeti top ‘+ Homonuclear diatomic molecules (such as H2, 02, Nz , Cl;) — have zero dipole (non polar) - have zero change of dipole during the rotation, hence NO interaction with radiation - hence homonuclear diatomic molecules are microwave inactive * Heteronuclear diatomic molecules (such as HCI, HF, CO) — have permanent dipolemoment (polar compound) - change of dipole occurs during the rotation — hence interaction with radiation takes place — Therefore, heteronuclear diatomic molecules are microwave activ2.3 DIATOMIC MOLECULES 2.3.1 The Rigid Diatomic Molecule ee | Figure 2.1 A rigid diatomic molecule treated as two masses, m, and m,, joined by a rigid bar of length ro =r, + r2- We start with this, the simplest of all linear molecules, shown in Fig. 2.1. Masses m, and m, are joined by a rigid bar (the bond) whose length is roan th (2.5) The molecule rotates end-over-end about a point C, the centre of gravity: this is defined by the moment, or balancing, equation: my ry = mary 26)The moment of inertia about C is defined by: T=myri+mr3 = mzryry t+ myryrz (from (2.6)) = ryra(m, + m2) (2.7) But, from (2.5) and (2.6): myn, = mzr2 = m{ro — 11) therefore, n= Mato and n= eo (2.8) m, +m, m, +m, Replacing (2.8) into (2.7): St a ura (2.9) where we have written «= m,m,/(m, +m), and 4 is called the reduced mass of the system. Equation (2.9) defines the moment of inertia con- veniently in terms of the atomic masses and the bond lengih.By the use of the Schrédinger equation it may be shown that the rotational energy levels allowed to the rigid diatomic molecule are given by the expression: re E,= rar] J(J + 1) joules where J = 0, 1, 2,... (2.10) In this expression h is Planck’s constant, and I is the moment of inertia, either J, or Ic, since both are equal. The quantity J, which can take integral values from zero upwards, is called the rotational quantum number: its re- striction to integral values arises directly out of the solution to the Schré- dinger equation and is by no means arbitrary, and it is this restriction which effectively allows only certain discrete rotational energy levels to the molecule.Equation (2.10) expresses the allowed energies in joules; we, however, are interested in differences between these energies, or, more particularly, in the corresponding frequency, v = AE/h Hz, or wavenumber, # = AE/hc cm™~', of the radiation emitted or absorbed as a consequence of changes between energy levels. In the rotational region spectra are usually discussed in terms of wavenumber, so it is useful to consider energies expressed in these units. We write: Ey he = BaF where c, the velocity of light, is here expressed in cm s~', since the unit of wavenumber is reciprocal centimetres. Equation (2.11) is usually abbreviated to: €, = BIJ + 1)cm™! V=0, 1, 2,...) (2.12) where B, the rotational constant, is given by mi h © 817 Ig “(9 =0,1,2,...) (2.11) im? (2.13) in which we have used explicitly the moment of inertia J,. We might equally well have used J, and a rotational constant C, but the notation of (2.13) is conventional.From Eq. (2.12) we can show the allowed energy levels diagram- matically as in Fig. 2.2. Plainly for J = 0 we have ¢, = 0 and we would say that the molecule is not rotating at all. For J = 1, the rotational energy is €, = 2B and a rotating molecule then has its lowest angular momentum. We may continue to calculate e, with increasing J values and, in principle, there is no limit to the rotational energy the molecule may have. In practice, of course, there comes a point at which the centrifugal force of a rapidly rotating diatomic molecule is greater than the strength of the bond, and the molecule is disrupted, but this point is not reached at normal temperatures.Fig. 2.2 Fig. 2.3 QO 4B sp 2B Se J 5 | i, 6 ——_____—_ 428 6 | | 5 308 | 5 | roe | 4 . | 3 ——————_ 128 | 3 | 2 1 | 0 | | 2B 6B «10B Figure 2.2. The allowed rotational energy levels of a rigid diatomic molecule. Figure 2.3 Allowed transitions between the energy levels of a rigid diatomic molecule and the spectrum which arises from them.We now need to consider differences between the levels in order to discuss the spectrum. If we imagine the molecule to be in the J = 0 state (the ground rotational state, in which no rotation occurs), we can let incident radiation be absorbed to raise it to the J =| state. Plainly the energy absorbed will be: bya, — fya9 = 2B—-0=2B cm"! and, therefore, Tyeonse1 =2B cm7! (2.14) In other words, an absorption line will appear at 2B cm~'. If now the molecule is raised from the J = | to the J = 2 level by the absorption of more energy, we see immediately: Vymtagar = Eynr — Ear =6B—2B=4B cm"! (2.15)In general, to raise the molecule from the state J to state J + 1, we would have: Tyoy41 = BU + IMJ + 2)— BI +1) (= BL? 4342-249) or By .y41 = 2B + 1) m=! (2.16) Thus a stepwise raising of the rotational energy results in an absorption spectrum consisting of lines at 2B, 4B, 6B, ..., cm~', while a similar lower- ing would résult in an identical emission spectrum. This is shown at the foot of Fig. 2.3.In deriving this pattern we have made the assumption that a transition can occur from a particular level only to its immediate neighbour, either above or below: we have not, for instance, considered the sequence of transitions J =0— J =2—J=4.... In fact, a rather sophisticated appli- cation of the Schrédinger wave equation shows that, for this molecule, we need only consider transitions in which J changes by one unit—all other transitions being spectroscopically forbidden. Such a result is called a selec- tion rule, and we may formulate it for the rigid diatomic rotator as: Selection rule: AJ = +1 (2.17) Thus Eq. (2.16) gives the whole spectrum to be expected from such a mol- ecule,Example: The first rotational line in the rotational spectrum of CO is observed at 3.84235 cm”. Calculate the rotational constant (B) and bond length of CO. The relative atomic weight C =12.00 and O = 15.9994, the absolute mass of H= 1.67343x10-27 kg.Tu, =3.8425=2B B=1.92118 cm™ =h , 7 82° Be 6.626 x 10°* 82° x2.99793x 10" xB =14.5695x10" kg.m? Teo = _19.92168x 26.56136 x107* 46.48303 x 10°?” 2 =4co ~1.9799% 107° sm? “a So, ‘eo =0.113 nm = 1.131 A? =11.38365 kg meIntensity of rotational spectral lines (Population of energy levels) Number of degenerated energy levels Boltzmann distribution Population of energy levels is affected by; 1- Boltzmann distribution 2- Number of degenerated energy levels (levels which have the same energies)2.3.2. The Intensities of Spectral Lines normal gas sample, there will be different numbers of molecules in each level to begin with, and therefore different total numbers of molecules will carry out transitions between the various levels. In fact, since the intrinsic probabilities are identical, the line intensities will be directly proportional to the initial numbers of molecules in cach level. 0.35 Rotational Spectrum of HCL Absorbance a Wavenumber emThe first factor governing the population of the levels is the Boltzmann distribution (cf. Sec. 1.7.2). Here we know that the rotational energy in the lowest level is zero, since J = 0, so, if we have No molecules in this state, the number in any higher state is given by: Nj/No = exp (—E,/kT) = exp {—BhcJ(J + 1)/kT} (2.18) where, we must remember, ¢ is the velocity of light in cm s~* when B is in cm‘. A very simple calculation shows how N s Varies with J; for example, taking a typical value of B=2cm~', and room temperature (say T = 300 K), the relative population in the J = 1 state is: Ni 2 x 6-63 x 10784 x 3x 10! x 1x 2 No ur 1-38 x 10-7? x 300 = exp (—0-019) = 0.98“ 1-Boltzmann distribution The number of molecules in the first state =N, The number of molecules in any higher state = N, Ny o-eyiet =e iv/kT) = eter kT) N, &; =v=BJ(J+1) So, YF _ e Bhar J)y AT e BI helkT oO The population of the state decreases as the J —value increases.Example; For HCl, 2B = 21.2 > B = 10.6, T=300 K, h=6.626x1074 J.s, kK=1.38x10°23 J/K, c = 3x 107 cm/s y=0> Neuen1 N, 10.6x6.63x1 07°4x3x10'° ~ o J=L>5 Me e 138107300 yon) > N, =e 0.0509(J+) = 0.903 N. ~ J a2, =e! = 0.7367 N, ° 2- Make another calculations with B = 5Nu decreases with increasing J o and with higher B The Boltzmann distribution alone does not fit the shape of the spectra so, degeneracy of the states is required.exp(— BJU + Ihe/kT) Rotational quantum number J Figure 24 The Boltzmann populations of the rotational energy levels of Fig. 2. The diagram thas been drawn taking values of B= Sand 10em~* and T = 300 K in Eq. (2.18),“ 2-Degeneracy The existence of more than two energy states having the same energy. Kinetic energy (K.E) in rotational motion =% I.w2 and since, angular momentum (P) =I.w_ then; 2 2 2 2; Ixla I-o@ P E=—— = ——_ = — = _ 2r 2r 2r eee 2 2 hm J(J+1 gat J(J+)) 2EI= i a p2 4n2 4a = JJ (J+1 - = JJ (J +1) unit. ‘ — is the angular momentum unit. 2aFigure 2.6(a) and (b) shows the situation for J = 2(P = \/6) and J =3 (P = 2,/3) with fivefold and sevenfold degeneracy respectively, In general it may readily be seen that each energy level is 2J + 1-fold degenerate. Thus we see that, although the molecular population in each level decreases exponentially (Eq. (2.18)), the number of degenerate levels avail- able increases rapidly with J. The total relative population at an energy E, will plainly be: Population oc (2 + 1) exp (~E,/kT) (2.20) diminishes. Differentiation of Eq. (2.20) shows that the population is a max- imum at the nearest integral J value to: kT 1 i ion, Jim, J (2.21 Maximum population: J pice a (2.21)For J =1 = Pis quantized, so it takes a directions such that the value of P along the reference direction are (-1, 0, +1). = Number of degeneracy is 2J+1=3 Reference directionForJ=2 = (-2, -1, 0, 1, 2) . P= JfJ(J+l degeneracy. 2 = Ve=2.44 = Number of 32 degeneracy is 2, wes) 23 +1=2x2+1=5 go — “1 a,Population of Rotational Energy Levels No _ -(a/eT)_ (hee seT) N, ° -e@ Boltzmann distribution expl-BU(J+1)hc/AT } ° 2 4 6 8 10 Rotational Quantum Number, J Orientation of the angular momentum, P, is quantized. This results in (2J+1}fold degeneracy of the energy levels.Populationee (25 +1)-e(42/*T) where AE= hee,= he Bu(J+1) B=10.6 cm™ (2d-+ 1 )expf-Bs (J+ 1)NC/KT ] Rotational Quantum Number, J(21+1) expl~ BU + Dae kT) O41 2 Ba Me Se 6 Fe Bilrs geno Rotational quantum number. J Figure 2.7 The total relative populations, including degeneracy, of the rotational energy levels of a diatomic molecule. The diagram has been drawn for the same conditions as Fig. 2.4.