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题名: Coadsorption of trimethyl phosphine and thiocyanate on colloidal silver: a SERS study combined with theoretical calculations
作者: Hu, Gengshen1;  Han, Difei1;  Jia, Guoqing1;  Chen, Tao1;  Feng, Zhaochi1;  Li, Can1
通讯作者: 李灿
关键词: trimethyl phosphine (TMP) ;  SCN(-) ;  surface-enhanced Raman scattering spectroscopy (SERS) ;  charge transfer ;  theoretical calculations
刊名: JOURNAL OF RAMAN SPECTROSCOPY
发表日期: 2009-04-01
DOI: 10.1002/jrs.2137
卷: 40, 期:4, 页:387-393
收录类别: SCI
文章类型: Article
部门归属: 5
项目归属: 503
产权排名: 1;1
WOS标题词: Science & Technology ;  Technology
类目[WOS]: Spectroscopy
研究领域[WOS]: Spectroscopy
英文摘要: The adsorption of trimethyl phosphine (TMP) on colloidal silver has been investigated by means of surf ace-enhanced Raman scattering spectroscopy (SERS). On the basis of surface selection rules, it is deduced from the SERS results that TMP adsorbs on silver surface via its P atom. The electron donor effect of TMP can be sensitively probed by the coadsorbed SCN(-). The Raman wavenumber of vCN of the adsorbed SCN(-) shifts to lower wavenumbers when TMP is coadsorbed with SCN(-) and the red shift of C N stretching wavenumber is found to increase with increasing surface coverage of TMP. This could be explained in terms of the electron donor effect of TMP. Density functional theory (DFT) calculations further confirm the experimental results that the charge transfer is from TMP to silver surface rather than reversely. Natural bond orbital (NBO) analysis indicates that the red shift of C N stretching mode is due the increase of electronic populations of pi* orbital of C N bond induced by coadsorbed TMP, consequently the C N bond is weakened, and the vCN shifts to lower wavenumbers. An NBO analysis also indicates that the conjugated effect between S atom and C N bond could easily make the charge transfer from silver surface to C N bond. Copyright (C) 2008 John Wiley & Sons, Ltd.
关键词[WOS]: SURFACE-ENHANCED RAMAN ;  DENSITY-FUNCTIONAL THEORY ;  VIBRATIONAL FREQUENCIES ;  GOLD ELECTRODES ;  AB-INITIO ;  IN-SITU ;  RH/SIO2 CATALYST ;  PPH3 LIGAND ;  SPECTROSCOPY ;  COMPLEXES
语种: 英语
原文出处: 查看原文
WOS记录号: WOS:000265547600007
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/102475
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China

Recommended Citation:
Hu, Gengshen,Han, Difei,Jia, Guoqing,et al. Coadsorption of trimethyl phosphine and thiocyanate on colloidal silver: a SERS study combined with theoretical calculations[J]. JOURNAL OF RAMAN SPECTROSCOPY,2009,40(4):387-393.
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