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OrientationalDynamics in Sum Frequency SpectroscopicLine Shapes.
- Source :
-
Journal of Physical Chemistry B . Dec2013, Vol. 117 Issue 49, p15833-15842. 10p. - Publication Year :
- 2013
-
Abstract
- Wepresent a general response function formalism describing thecontribution of orientational dynamics of molecules at interfacesto spectroscopic line shapes in vibrational sum frequency generation(SFG). When reorientation occurs on the time scale comparable to vibrationaldephasing, its dynamics can be extracted from polarization-selectedSFG spectral line shapes. Unique features of orientational motionat interfaces are (1) the anisotropic case-specific equilibrium orientationaldistribution and (2) possible dynamic anisotropy (e.g., differentin-plane versus out-of-plane relaxation rates), both of which mustbe taken into account. Within the small-step rotational diffusionmodel, we present solutions for two cases, the weak-confinement model,applicable when the deviations from the isotropic case are not severe,and the wobbling-in-a-cone model, which considers a hard-wall orientingpotential. SFG line shapes are calculated for a rod-like chromophoreas a function of the rotational diffusion rate. For certain equilibriumorientational distributions, orientational dynamics may result inanomalous bi-Lorentzian line shapes (two Lorentzians of differentwidths centered and the same frequency). [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 15206106
- Volume :
- 117
- Issue :
- 49
- Database :
- Academic Search Index
- Journal :
- Journal of Physical Chemistry B
- Publication Type :
- Academic Journal
- Accession number :
- 92984880
- Full Text :
- https://doi.org/10.1021/jp408048a