A Closer Look at Tip-Enhanced Raman Chemical Reaction Nanoimages

O’Callahan, Brian T.; El-Khoury, Patrick Z.

doi:10.1021/acs.jpclett.2c00574

A Closer Look at Tip-Enhanced Raman Chemical Reaction Nanoimages

Journal Article · Tue Apr 26 00:00:00 EDT 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c00574· OSTI ID:2474988

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Tip-enhanced Raman spectroscopy (TERS) is a powerful technique that enables ultrahigh spatial resolution and ultrasensitive chemical imaging. This technique’s ability to track plasmon-induced/enhanced chemical reactions in real space has gained increasing popularity in recent years. Here, in this study, we expose inherent difficulties associated with assigning TERS signatures that accompany chemical transformations. Namely, distinct selection rules as well as the possibility of multiple physical processes/chemical reaction pathways complicate spectral assignments and necessitate caution in assigning the experimental observables. We illustrate the latter using 4,4'-dimercaptostilbene-functionalized plasmonic silver nanocubes, wherein we identify the TERS signatures of product formation, molecular charging, multipolar Raman scattering, and preferred molecular orientations that all lead to distinct and assignable spectral patterns.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2474988

Report Number(s):: PNNL-SA--170830

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 17 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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