# Diatomic molecules The Rigid Diatomic molecule e g d ato c o ecu e

Simplest of all linear molecules

Masses m1 and  m2 are joined by a rigid bar whose length is  j y g g 1  R = r1 + r2 The molecule rotates end‐over‐end about the centre of  gravity: defined as the balancing equation: m1r1= m2r2 .

The moment of inertia about the centre of mass is defined by: y I = m1r12 + m2r22 But. m1r1 = m2r2 = m2( – r1) (R So.  m2 R r1 = m1 + m2 and  m1 R r2 = m1 + m2 . (m1r1 = m2r2) ( = m2r2r1 + m1r1r2 = r1r2(m1 + m2) ( Now.

I = r1r2 (m1 + m2 ) m2 R r1 = m1 + m2 m1 R r2 = m1 + m2 m1m2 2 2 I= R = μR m1 + m2 m1m2 μ= m1 + m2 Reduced mass of the system .

then we need two angles θ and φ to characterize it.If the molecule rotates in three dimensions. We will take these to be the angles in the spherical polar coordinate system (θ is the polar angle and φ is the azimuthal angle). .

2. …….Schrödinger Equation  gives the rotational energy levels  Schrödinger Equation gives the rotational energy levels allowed to the rigid diatomic molecule. either IA or IB. since both are  equal. 2 2 joules The rotational quantum number I is the moment of inertia. 1. h E J = 2 J ( J + 1) = J ( J + 1) 8π I 2I h J = 0. l .

Hence.…. each rotational energy level has a degeneracy  2J+1 Hence each rotational energy level has a degeneracy 2J 1 . namely  angular part of the hydrogen atom wave functions namely the spherical harmonics.φ). YJm(θ. J. m = ‐J.The rotational wave functions are exactly the same as the  angular part of the hydrogen‐atom wave functions. Here the quantum number m characterizes the z‐component  Here the quantum number m characterizes the z‐component of the molecules angular momentum.

the  molecule can undergo a transition between rotational energy  levels.  levels What is the energy difference between the energy level with  What is the energy difference between the energy level with J+1 and the energy level with J? .If the molecule absorbs a photon of frequency  the If the molecule absorbs a photon of frequency ν.

the frequencies at which transitions can occur are  Therefore the frequencies at which transitions can occur are given by  The rotational constant B is  given by:   .Therefore.

f b The energy in this unit is given as: EJ h εJ = = 2 J ( J + 1) cm -1 hc 8π Ic EJ -1 εJ = = BJ ( J + 1) cm hc (J = 0. . ...In the rotational region spectra are usually discussed in terms  of wavenumber. 1.) (J = 0..) h B= 2 cm -1 8π I B c ...... 1. 2. 2.

For J=0. εJ=0 The molecule is not  rotating at all. εJ=2B lowest angular  momentum.  of a rigid diatomic molecule The rotating  molecule has its  For J=1.The allowed rotational energies  of a rigid diatomic molecule. .

.The Rotational Spectrum Molecule at J=0 (Ground state Rotational State) ( ) No rotation occurs The molecule can absorb the incident radiation to move to J = 1 state  The energy absorbed will be: h b b d ll b εJ=1 ‐ εJ=0 = 2B – 0 = 2B cm‐1 ν J = 0 → J =1 = 2B cm -1 An absorption line will  appear at 2B cm‐1.

y g gy ν J =1→ J = 2 = ε J = 2 − ε J =1 = 6 B − 2 B = 4 B cm In general: To raise the molecule from J to J+1 To raise the molecule from J to J+1 -1 ν J → J +1 = B ( J + 1)( J + 2 ) − BJ ( J + 1) = B J 2 + 3J + 2 − J 2 + J = 2 B ( J + 1) cm -1 [ ( )] .Molecule is raised from J=1 to J=2 by absorbing more energy.

Allowed transitions between the energy levels of a rigid diatomic molecules and the spectrum which arises from them. .

Application of Schrödinger wave equation shows that: For the diatomic molecules we need to consider transitions in which J changes by one unit. .To obtain the rotational spectrum for diatomic molecules: Assumption: Transition can take place from a particular level to its immediate neighbour. either above or below. Other transitions are spectroscopically forbidden.

eg. N2. HCl. O2. CO. The rotational spectrum is not observed if the molecule is homonuclear.The Selection Rule For rigid diatomic rotators: ΔJ=±1 The Th rotational spectrum is observed only if the molecule i l i b d l h l l is asymmetric (heteronuclear). eg. .

The rotation about the bond axis was rejected. Such transitions d not occur under normal S ht iti do t d l conditions. For 2 F such t h transitions th iti there will b no di l change. Result i no spectrum. The Th molecule requires a h l l i huge amount of energy t t f to be raised from J=0 to J=1 state. The energy levels will be extremely widely spaced. R lt is t 2.HOMONUCLEAR DIATOMICS Reasons for not observing a spectrum: 1. ill be dipole h . The Th moment of inertia is very small about th b d t f i ti i ll b t the bond.

Hi Bronclif ! HI BrONClF Hydrogen H d Iodine Bromine Oxygen g Nitrogen Chlorine Fluorine .HOMONUCLEAR DIATOMICS Seven molecules do not show rotational spectrum.