By C.H. Bamford and C.F.H. Tipper (Eds.)

ISBN-10: 0444408614

ISBN-13: 9780444408617

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2 Anharmonic oscillator. A consequence of the introduction of the anharmonic oscillator is that the distance between consecutive energy levels is not equal. In spectroscopy, this is seen by the occurrence of sum peaks and overtones. 3 13 Energy Levels and Group Frequencies The result of the Schr¨odinger equation for a particle in a box tells us that only a limited number of energy levels are allowed: Eν = (ν + 1/2) • hνv (ν = 0, 1, 2, . . 626075540 · 10−34 J · s) and νv the molecular vibrational frequency.

In reality, intensity is not measured in exactly one direction, but should be integrated over a solid angle (centred around θ ) and this expression should be integrated over this solid angle. 30 ), p0 is independent of the orientation. 29) the absolute wave number is used ν = 1 = ν , opposite to the Raman λ c ν ±ν wave number νv = νcv . The relation between both is: ν = ν0 ± νv = 0 c v , with ν0 laser frequency. Theoretical Aspects 21 why UV-Raman spectroscopy is an interesting technique. 30 ) it can be seen that the measured intensity is proportional to the square of the amplitude of the polarisability and we see as well a strong dependence on the orientation (sin2 θ ) of the measured Raman effect.

In Raman spectroscopy, two types of measurement geometry are often encountered: • the traditional 90◦ geometry, where the scattered light is measured perpendicular to the incident beam; • the back-scattering geometry, where the light is measured that is back-scattered in the direction of the laser. The electrical field vector E of the incident light can be decomposed in two vectors, perpendicular to each other: Ey and Ez ; since the field vector is perpendicular to the direction of propagation, the third component Ex = 0.

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Decomposition and Isomerisation of Organic Compounds by C.H. Bamford and C.F.H. Tipper (Eds.)

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