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Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds
Published on: October 12, 2018
Effective conjugation and Raman intensities in oligo(para-phenylene)s: a microscopic view from first-principles
Georg Heimel1, Dieter Somitsch, Peter Knoll
1School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, 30332-0400, USA. george.heimel@chemistry.gatech.edu
Abstract:
Electron-phonon coupling in oligo(para-phenylene)s is addressed in terms of the off-resonance Raman intensities of two distinct modes at 1220 and 1280 cm(-1). On the basis of Albrecht's theory, vibrational coupling and Raman intensities are calculated from first-principles quantum-chemical methods. A few-state model is used to evaluate the dependence of the mode intensities on oligomer length, planarity, and excitation wavelength. The link between electron delocalizationconjugation and Raman intensities is highlighted. Extending on prior studies, the present work focuses on providing an in-depth understanding of the origin of this correlation in addition to reproducing experimental findings. The model applied here allows us to interpret the results on a microscopic, quantum-mechanical basis and to relate the observed trends to the molecular orbital structure and nature of the excited states in this class of materials. We find quantitative agreement between the results of the calculations and those of measurements performed on oligo(para-phenylene)s of various chain lengths in the solid state and in solution.
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