Intramolecular couplings and the secondary structure of CC stretching bands

Vojta, Danijela; Baranović, Goran

doi:10.1016/j.vibspec.2010.01.014

Cited by 5 publications

(1 citation statement)

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“…The observed activated temperature dependence of both narrowing and frequency shifting of the peaks is characteristic of vibrational dephasing. Exchange modes mediating vibrational dephasing have been previously assigned to low energy intra- or inter-molecular vibrations, frustrated rotations, translations, or substrate phonons based upon the extracted E A and the frequencies of available modes. ,,, The four vibrational modes analyzed in Table exhibit values of E A corresponding to specific frequencies ranging from 270 to 590 cm –1 . A number of low energy torsions of MG are available near the observed E A , which can act as exchange modes, whereas phone modes of Au with energies limited to ≤160 cm−1 are less likely to contribute .…”

Section: Discussionmentioning

confidence: 99%

Variable-Temperature Tip-Enhanced Raman Spectroscopy of Single-Molecule Fluctuations and Dynamics

et al. 2015

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Structure, dynamics, and coupling involving single-molecules determine function in catalytic, electronic or biological systems. While vibrational spectroscopy provides insight into molecular structure, rapid fluctuations blur the molecular trajectory even in single-molecule spectroscopy, analogous to spatial averaging in measuring large ensembles. To gain insight into intramolecular coupling, substrate coupling, and dynamic processes, we use tip-enhanced Raman spectroscopy (TERS) at variable and cryogenic temperatures, to slow and control the motion of a single molecule. We resolve intrinsic line widths of individual normal modes, allowing detailed and quantitative investigation of the vibrational modes. From temperature dependent line narrowing and splitting, we quantify ultrafast vibrational dephasing, intramolecular coupling, and conformational heterogeneity. Through statistical correlation analysis of fluctuations of individual modes, we observe rotational motion and spectral fluctuations of the molecule. This work demonstrates single-molecule vibrational spectroscopy beyond chemical identification, opening the possibility for a complete picture of molecular motion ranging from femtoseconds to minutes.

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