Journal
NANO LETTERS
Volume 16, Issue 12, Pages 7774-7778Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.nanolett.6b03958
Keywords
Ultrahigh vacuum; tip-enhanced Raman spectroscopy; conformational isomers; nanoscale chemical imaging; single molecule spectroscopy
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Funding
- National Science Foundation Center for Chemical Innovation [CHE-1414466]
- Department of Energy Office of Basic Energy Sciences (SISGR Grant) [DE-FG02-09ER16109]
- National Science Foundation Materials Research Science and Engineering Center [NSF DMR-1121262]
- Air Force Office of Scientific Research MURI [FA9550-14-1-0003]
- NSERC Postdoctoral Fellowship
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1414466] Funding Source: National Science Foundation
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Tip-enhanced Raman spectroscopy (TERS) combines the ability of scanning probe microscopy (SPM) to resolve atomic-scale surface features with the single-molecule chemical sensitivity of surface-enhanced Raman spectroscopy (SERS). Here, we report additional insights into the nature of the conformational dynamics of a free-base porphyrin at room temperature adsorbed on a metal surface. We have interrogated the conformational switch between two metastable surface-mediated isomers of meso-tetrakis(3,5-ditertiarybutylphenyl)-porphyrin (H2TBPP) on a Cu(111) surface. At room temperature, the barrier between the porphyrin ring buckled up/down conformations of the H2TBPP-Cu(111) system is easily overcome, and a 2.6 angstrom lateral resolution by simultaneous TERS and STM analysis is achieved under ultrahigh vacuum (UHV) conditions. This work demonstrates the first UHV-TERS on Cu(111) and shows TERS can unambiguously distinguish the conformational differences between neighboring molecules with Angstrom-scale spatial resolution, thereby establishing it as a leading method for the study of metal-adsorbate interactions.
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