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제108회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Re-interpretation of b2-peaks in the SERS spectra of 4-aminobenzenethiol

2011년 8월 1일 15시 33분 06초
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금 <발표Ⅲ>
저자 및
최한규, 유현웅1, 이준호, 채승현, 이석중, 이태걸1, 김지환
고려대학교 화학과, Korea
1한국표준과학연구원 미래융합기술부, Korea
In the Surface Enhanced Raman Spectroscopy (SERS), 4-aminobenzenethiol (ABT) have served as the "probe" molecule, which have affected to research the electromagnetic (EM) and chemical (CHEM) enhancement mechanisms. In particular, the b2-peaks (9b, 3, and 19b) of the SERS spectra of ABT have been attributed to arise from the vibronic charge-transfer (CT) between Au or Ag surface and the ABT. Quite recently, however, Tian and co-workers [1] claimed that the b2-peaks are not the result of CT-enhanced spectra of ABT. Instead, these peaks arise from the 4,4’-dimercaptoazobenzene (DMABs) that are produced by the oxidative coupling of two ABTs. Their claim is under intense debate currently. Herein, we studied spatially and temporally resolved SERS spectra of ABTs on Ag thin film (thickness of 10 nm), to investigate such claim. Also, we present a series of additional evidences. This results strongly support that the b2-peaks of ABTs do not arise from the CT-enhancement: (1) the b2-peaks can be locally "activated" (i. e. turned on) irreversibly with focused laser radiation; (2) the TOF-SIM spectrometry on the activated region show depletion of ABT-Ag+ ions; and finally (3) the spatially resolved FT-IR spectra of the activated region show two pronounced peaks at 1377 cm-1 and 1460 cm-1, both of which can be assigned to the stretching mode of N=N bond. While the above evidences do not disprove the existence of CT or CHEM enhancement in general, the results do show that previous interpretations of the spectra of ABTs should be re-interpreted.

References [1] Yi-Fan Huang, Hong-Ping Zhu, Guo-Kun Liu, De-Yin Wu, *Bin Ren, * and Zhong-Qun Tian, J. AM. CHEM. SOC. 2010, 132, 9244-9246