Adsorption geometries; Experimental spectra; Geometry optimization; Isolated molecules; Molecular identification; Normal mode analysis; Overall accuracies; Surface enhanced Raman spectroscopy; Electronic, Optical and Magnetic Materials; Energy (all); Physical and Theoretical Chemistry; Surfaces, Coatings and Films; General Energy
Abstract :
[en] Surface-enhanced Raman spectroscopy probes adsorbates on a plasmonic substrate and offers high sensitivity with molecular identification capabilities. In this study, we present a refined methodology for considering the supporting substrate in the computation of the Raman spectra. The supporting substrate is taken into account by employing a periodic slab model when doing the geometry optimization and normal mode analysis, and then the Raman spectrum is calculated for the isolated molecule but with the normal modes from the surface structure. We find that the interaction with the surface induces internal distortion in the molecule, and spectral shifts in the computed Raman spectrum. By comparing a low temperature surface-enhanced Raman spectroscopy measurement of Rhodamine 6G (R6G) with the computed Raman spectra of a series of adsorption geometries, we propose that the binding state captured in the experiment tends to possess the least internal distortion. This binding state involves upward orientation of ethylamine on R6G, and our calculations indicate that this is the lowest energy adsorption structure. Following this route, it is possible to infer both a molecular orientation and an adsorption geometry of the molecule from its Raman spectrum. Importantly, we note that, if the substrate correction is established to play a role, we also discuss that this corrected approach still has several shortcomings that significantly limit its overall accuracy in comparison with experimental spectra.
Disciplines :
Chemistry
Author, co-author :
Van Dyck, Colin ; Université de Mons - UMONS > Faculté des Sciences > Service Chimie Physique Théorique
Fu, Bo; Department of Physics and Astronomy, Northwestern University, Evanston, United States
Van Duyne, Richard P. ; Department of Chemistry, Northwestern University, Evanston, United States
Schatz, George C. ; Department of Chemistry, Northwestern University, Evanston, United States
Ratner, Mark A.; Department of Chemistry, Northwestern University, Evanston, United States
Language :
English
Title :
Deducing the Adsorption Geometry of Rhodamine 6G from the Surface-Induced Mode Renormalization in Surface-Enhanced Raman Spectroscopy
Publication date :
11 January 2018
Journal title :
Journal of Physical Chemistry. C, Nanomaterials and interfaces
Government of Canada U.S. Department of Defense University of Alberta Government of Alberta
Funding text :
We thank Dr. Fredy Aquino for the help with the AOResponse module of the NWChem package. This work was supported by the Air Force Office of Scientific Research MURI project (FA9550-14-1-0003). C.V.D. thanks Dr. Lindsey Madison for useful discussion and the support by the National Institute for Nanotechnology, which is operated as a partnership between the National Research Council, Canada, the University of Alberta, and the Government of Alberta. We gratefully acknowledge the computational resources from the Quest high performance computing facility at Northwestern University and the Extreme Science and Engineering Discovery Environment (XSEDE) program which is supported by National Science Foundation grant number ACI-1053575. We also acknowledge the Center for Nanoscale Materials (Argonne National Lab), an Office of Science user facility, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
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