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* * - Resulting Raman Spectrum Probability of Emission % Observed Intensity Raleigh scattering Stokes anti-Stokes difference in population of energy levels of vibrational transitions Intensity of Raman lines are 0.001% intensity of the source Lower energy higher energy 3.) Active Raman Vibrations: - need change in polarizability of molecule during vibration - polarizability related to electron cloud distribution example: O = C = O IR inactive Raman active O = C = O IR active Raman inactive IR Raman are complimentary. Can be cases where vibration is both IR Raman active (eg. SO2 – non-linear molecule) In general: IR tends to emphasize polar functional groups (R-OH, , etc.) Raman emphasizes aromatic carbon backbone (C=C, -CH2-, etc.) - Raman does not “see” many common polar solvents can use with aqueous samples – advantage over IR Raman frequency range: 4000 -50 cm-1(Stokes and anti-stokes) The simplest real vibrating system:a diatomic molecule Reduced mass displacement x1 x2 m1 m2 K Where: Just like Hooke’s law: F=kX Scattering of radiation from a diatomic molecule ? Induced dipole moment: For a small amplitude of vibration, the polarizability a is a linear function of q: Rayleigh scattering Stokes scattering Anti-Stokes scattering ? Example 1: the vibration modes of CO2 Raman Active IR Active IR Active Example 2: the vibration modes of H2O All the modes are both Raman IR Active Normal vibrations of CH2Cl2 n = stretching d = bending Sample I0(n) I(n) n0 n0 - Rayleigh Sample n0 ? nM - Raman IR Spectrography - Absorption Laser detector Laser detector - comparison of Raman and IR Spectra 4.) Instrumentation: - Basic design i. ) Light source: - generally a laser to get required intensity of light for reasonable S/N ? Raman scattering is only 0.001% of light source - Doesn’t have to be in IR region, since look at changes around central peak. ? visible source used because of high i