Citation: SUN Lei, BAI Fu-Quan, ZHANG Hong-Xing. Theoretical Investigation of Chemically Enhanced Mechanism of SERS Spectroscopy for Ag/MPH/TiO₂ System[J]. Acta Physico-Chimica Sinica, ;2011, 27(06): 1335-1340. doi: 10.3866/PKU.WHXB20110602 shu

Theoretical Investigation of Chemically Enhanced Mechanism of SERS Spectroscopy for Ag/MPH/TiO₂ System

1.
State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, P. R. China

Received Date: 28 February 2011
Available Online: 15 April 2011
Fund Project: 国家自然科学基金(20973076, 21003057)资助项目 (20973076, 21003057)

A chemically enhanced mechanism of surface-enhanced Raman scattering (SERS) spectroscopy was investigated using density functional theory (DFT). We studied the Raman spectra of the Ag₁₃/MPH and Ag₁₃/MPH/TiO₂ systems under 514.5 nm excitation. We found that the intensities of the non-totally symmetric vibration modes were selectively enhanced after TiO₂ was introduced into the Ag₁₃/MPH system. By analyzing the ground state and excited states of the charge transfer (CT) complex we found that the system gave a photoinduced CT state from Ag to the MPH-TiO₂ complex when the excitation wavelength exceeded the optical absorption threshold (635 nm) of the MPH-TiO₂ complex. The selective enhancement of the b₂ modes in the SERS spectra probably originates from the Herzberg-Teller mechanism through the coupling of the corresponding modes with the CT transition. Our theoretical results support the experimental results and also define the adsorption threshold of the CT complex clearly while providing an intelligible physical explanation for the laser wavelength-dependent SERS phenomenon.
- Surface-enhanced Raman scattering,
- Density functional theory,
- Charge transfer complex,
- Chemically enhanced mechanism
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沈阳化工大学材料科学与工程学院沈阳 110142

Theoretical Investigation of Chemically Enhanced Mechanism of SERS Spectroscopy for Ag/MPH/TiO2 System

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通讯作者: 陈斌, bchen63@163.com

Theoretical Investigation of Chemically Enhanced Mechanism of SERS Spectroscopy for Ag/MPH/TiO₂ System