Frequency distributions, vibrational line shapes

Vibrational spectroscopy can help us escape from this predicament due to the exquisite sensitivity of vibrational frequencies, particularly of the OH stretch, to local molecular environments. Thus, very roughly, one can think of the infrared or Raman spectrum of liquid water as reflecting the distribution of vibrational frequencies sampled by the ensemble of molecules, which reflects the distribution of local molecular environments. This picture is oversimplified, in part as a result of the phenomenon of motional narrowing The vibrational frequencies fluctuate in time (as local molecular environments rearrange), which causes the line shape to be narrower than the distribution of frequencies [3]. Thus in principle, in addition to information about liquid structure, one can obtain information about molecular dynamics from vibrational line shapes. In practice, however, it is often hard to extract this information. Recent and important advances in ultrafast vibrational spectroscopy provide much more useful methods for probing dynamic frequency fluctuations, a process often referred to as spectral diffusion. Ultrafast vibrational spectroscopy of water has also been used to probe molecular rotation and vibrational energy relaxation. The latter process, while fundamental and important, will not be discussed in this chapter, but instead will be covered in a separate review [4],... 

High resolution studies by conventional spectroscopy are genuinely hampered by Doppler-broadening of the rotation-vibration lines in the low pressure regime. Individual Doppler-shifted frequencies contribute to the (normalized) Doppler-broadened line shape, due to the distribution of molecular velocities along the direction of observation... 

The widths of the Raman line for the BAM is determined by the distribution of lengths for undisturbed conjugations and a consequently resulting distribution of HOMO to LUMO transition energies. This distributions together with the dependence of the vibrational mode frequency on the size of the undisturbed regions detemine the shapes and to some extent even the positions for the Raman lines. The size dependence of the HOMO to LUMO transition is basically a particle in the box problem. This can be demonstrated nicely by a simple Hiickel type calculation for the HOMO to LUMO... 

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