Time-dependent theory of Raman scattering

  • Lee S
  • Heller E
  • 108


    Mendeley users who have this article in their library.
  • 642


    Citations of this article.


A time-dependent picture of vibrational Raman scattering in the weak field limit is presented. From this viewpoint we can separate the static effects. due to the coordinate dependence of the electronic transition dipole. from the dynamic effects that arise from wave packet propagation on the Bom-Oppenheimer surfaces. Away from resonance. the energy uncertainty relation gives the propagation time necessary to obtain the cross section as being inversely proportional to the mismatch of the excitation frequency with the excited surface. The wave packet. given by the initial vibrational wave function times the transition dipole. hardly moves on the excited surface when the excitation frequency is far from resonance. As the excitation frequency is tuned closer to resonance. the propagated wave packet samples a larger portion of the surface. Using the short time approximation to the propagator. we obtain formulas for the cross section that are applicable for Raman scattering by polyatomics. The short time approximation is expected to be good away from resonance independent of the nature of the surface. and also on resonance with a repulsive surface. For an attractive surface. the approximation gives the average resonant cross section useful in the case when the vibrational structures cannot be observed.

Get free article suggestions today

Mendeley saves you time finding and organizing research

Sign up here
Already have an account ?Sign in

Find this document


Cite this document

Choose a citation style from the tabs below

Save time finding and organizing research with Mendeley

Sign up for free