TY  - JOUR
AU  - Park, Kyoung-Duck
AU  - Muller, Eric A.
AU  - Kravtsov, Vasily
AU  - Sass, Paul M.
AU  - Dreyer, Jens
AU  - Atkin, Joanna M.
AU  - Raschke, Markus B.
TI  - Variable-Temperature Tip-Enhanced Raman Spectroscopy of Single-Molecule Fluctuations and Dynamics
JO  - Nano letters
VL  - 16
IS  - 1
SN  - 1530-6992
CY  - Washington, DC
PB  - ACS Publ.
M1  - FZJ-2016-04695
SP  - 479 - 487
PY  - 2016
AB  - 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.
LB  - PUB:(DE-HGF)16
UR  - <Go to ISI:>//WOS:000368322700074
C6  - pmid:26679007
DO  - DOI:10.1021/acs.nanolett.5b04135
UR  - https://juser.fz-juelich.de/record/818202
ER  -