By Bipattaran Paramanik Department of Chemistry New Alipore College “We need a spirit of victory, a spirit that will carry us to our rightful place under the sun, a spirit which can recognize that we, as inheritors of a proud civilization, are entitled to our rightful place on this planet. If that indomitable spirit were to arise, nothing can hold us from achieving our rightful destiny.” ON Sa532nm Laser 5321nm o> 532 nue rr os 5%, Ne 4, a ce ys, a % Hw 532nm® Whena beam of monochromatic radiation passes through a liquid or gaseous substance, it might get scattered. ® Either the frequency of the radiation is unchanged (Rayleigh scattering) or the scattered radiation has lower frequency (Stokes lines) or higher frequency (anti-Stokes lines). Elastic scattering: A small metal ball bouncing off the table without any loss of energy. Inelastic scattering: Asmall metal ball bouncing on a oscillating drum.® Either molecule take energy from the imping photon or give energy to the imping photon. (approximately 1 in 10 million) E Molecule goes to an excited state or comes to a lower energy level. 4 5 “in Deseat Ine Mt lon scattered light Molecular excitation E ‘exe e-@ | Vibration RotationElectronically ES Virtual energy states Vibrational energy states OrPNWs Infrared Rayleigh Stokes —_Anti-Stokes absorption scattering Raman Raman scattering scattering of ‘the radiation. © Let, Photon + Molecule = Complex for a very short time (1 fs). ® Molecules was in GS and complex formed then it comes to the GS state again : Rayleigh Scattering. Av= © Molecules was in GS and complex formed then it comes to the ES state again : Raman Scattering. Red shift of the Radiation. Av < 0 ® Molecules was in ES and complex . formed then it comes to the ES.» 6Distortion of the molecule by external electric field: Polarization Induced dipole moment, P=aE a = polarizability P depends on direction and magnitude of the electric field, E Oscillating electric field q= displacement coord. > Um = freq. of molecule Induced dipole moment: P =aE =a Egcos(27Vvo -t) For a small amplitude of vibration, the ace aoe @ polarizability @ is a linear function of q: re aa oas 2 > Paap Eo cos(2nv y+ (& Q ) +qocos(2rVv,, *t)- Eo cos(27 Vo «.8) = &q J 4-0 = ay Egcos(2rvg - t) + 4(2) qoEo[cos(2x{v9 — —y eee Rayleigh scattering Anti-Stokes scattering scatteringa . a ‘, e +O Raman Active Pa =O Raman Inactive E& Molecular vibration or rotation must cause a change in the component of molecular polarizability. Represented by Length of the axis polarizability eS O=8: Epraeona to Polanizability is atest the axis © @ esi the'éllipsoid Qs isTeast. * Like elasticity ©»The electron distribution in H,, for example, is more distorted when the field is applied parallel to the bond than when it is applied perpendicular to it, and we write a |) > a,. All Linear Molecules (diatomic homonuclear or heteronuclear) have Anisotropic Polarizabilities, and so are rotationally Raman active. Raman spectroscopy can be used to study many of the molecules that are inaccessible to microwave spectroscopy. Spherical rotors such as CH, and SF, however, are rotationally, Raman inactive as well as microwave inactive. Molecular collisions do not have to obey such restrictive selection rules.Same appearance of the polarizability ellipsoid to an observer, twice in every complete rotation. = (p, l@lp,,) ais an even function = . = w, and p,, either even or odd This leads to the Selection Rule AJ=Oort2 AJ=0 Rayleigh Scattering AJ=+ 2S branch €;=BJ(J+1)-D, J?(J+1)?incm* _[ Neglect centrifugal distortion] . » ForAJ =2 For AJ = -2 Rue Anti-Stok tae? Ae = B(4S46) Ac ;=-B(4J+6) SQ Jie On J) =071,2 Pr ai V= v.. + B (4J+6) J =o (+) for Anti-Stokes’ and (-) for stokesSStokes’ Lines Anti-Stokes’ Lines Sometimes 2 nuclear spin 4 have major 3 role 2 1 J=0 Rotational information of a Microwave Inactive molecule 4B 4B |<< 6B | op meloOnly those vibrational modes are Raman active for which ba #0 6q ® A molecule with little symmetry or no symmetry, all of its vibrational modes are Raman active. © But molecule with considerable symmetry, it is not so. e, =(v+ 1/2) v,-(v+1/2)? v, X, Selection Rule: Same as pure vibrational spectra. Av=+1,4+2,+3... 1. Forv=0 to 1 (Fundamental) =(1-2x,)¥, cm? 2. For v=0 to 2 (1 overtone) =2(1-3X, ve cm yas’ Very weak 3. For v =1 to 2 (Hot) =(1-4x,)¥, cmt ¥=¥,,$(-44)¥,. ‘ont Anti Stokes’ :Almost no Line(®) vq, bending mode Q Oe, Q — (©) "5, asymmetric stretching mode (2) Bw CD Fluctuation in the size of Ellipsoid oem ae Scissoring Direction of major axis changes wee marke(0%, stymmeie sterching mode | oe Remember : ‘ i size of axis = — a q = displacement Coordinate, here § Doubly degeneratedsymmetric C-O eee vy Stretch € > IR Inactive Raman Active Bend V2 & 5 IR Active Bana Inactive < < Asymmetric C-O stretch a H © In fact, even for molecules which do not possessa centie’ of symmetric modes are weak in IR and strongin Rajiian, whi and asymmetric modes are weak in Raman. oO 4 ae metry, as bendingIR and Raman spectroscopy are complementary to each other. However, there are differences.