电化学界面SERS光谱的密度泛函理论研究

doi:10.61558/2993-074X.3361

摘要/Abstract

摘要： 运用量子化学密度泛函DFT理论和拉曼光谱研究了吡啶在过渡金属(Ⅷ族)和币族金属(IB族)表面吸附的成键机理及其拉曼光谱的变化规律.总结了作者研究组有关吡啶-金属SERS体系的研究,并从化学成键机理和光驱电荷转移机理两个方面探讨了电化学界面SERS谱峰的频率位移和增强效应,解释了实验观测到的SERS光谱随金属电极材料、激发光波长以及电极电位变化的现象.

关键词: DFT, 吡啶, 表面增强拉曼光谱, 电化学界面, 吸附, 电荷转移

Abstract: Quantum chemical density functional theory and Raman scattering theory were used to study the bonding mechanism and surface-enhanced Raman spectroscopy of pyridine adsorbed on transition metals (Ⅷ group) and coinage metals (IB group) . SERS studies of pyridine-metal systems have been reviewed. Chemical bonding mechanism as well as photo-driven charge transfer mechanism was considered to investigate the vibrational frequency shift and the enhancement of SERS intensity in electrochemical interfaces. Our theoretical results can be used to interpret the SERS phenomena dependent on metals,excitation wavelengths,and applied potentials.

Key words: DFT, pyridine, surface-enhanced Raman spectroscopy, electrochemical interface, adsorption, charge transfer

中图分类号:

O657.1

赵刘斌, 吴德印, 任斌, 田中群, . 电化学界面SERS光谱的密度泛函理论研究[J]. 电化学（中英文）, 2010, 16(3): 334-342.

ZHAO Liu-bin, WU De-yin , REN Bin, TIAN Zhong-qun . Density Functional Theory Studies of Surface-Enhanced Raman Spectroscopy in Electrochemical Interfaces[J]. Journal of Electrochemistry, 2010, 16(3): 334-342.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3361

https://electrochem.xmu.edu.cn/CN/Y2010/V16/I3/334

参考文献

[1]Tian Z Q,Ren B,Wu D Y.Surface-enhanced Raman scattering:From noble to transition metals and from rough surfaces to ordered nanostructures[J].J Phys Chem B,2002,106:9463-9483. [2]Tian Zhong-qun(田中群).Issues of nanoscale science related to surface enhanced Raman spectroscopy[J].China Basic Science(中国基础科学),2001,3:4-10. [3]Wu D Y,Li J F,Ren B,et al.Electrochemical surface-enhanced Raman spectroscopy of nanostructures[J].Chem Soc Rev,2008,37:1025-1041. [4]Tian Z Q,Ren B.Adsorption and reaction at electro-chemical interfaces as probed by surface-enhanced Ra-man spectroscopy[J].Annu Rev Phys Chem,2004,55:197-229. [5]Moskovits M.Surface enhanced Raman scattering spec-troscopy[J].Rev Mod Phys,1985,57:783. [6]Campion A,Kambhampati P.Surface-enhanced Ramanscattering[J].Chem Soc Rev,1998,27:241-250. [7]Nie S M,Emery S R.Probing single molecules and sin-gle nanoparticles by surface-enhanced Raman scattering[J].Science,1997,275:1102-1106. [8]Kneipp K,Wang Y,Kneipp H,et al.Single molecule de-tection using surface-enhanced Raman scattering(SERS)[J].Phys Rev Lett,1997,78:1667-1670. [9]Otto A,Mrozek I,Grabhorn H,et al.Surface-enhanced Raman scattering[J].J Phys Condens Matter,1992,4:1143-1212. [10]Fleischmann M,Hendra P J,McQuillan A J.Raman spectra of pyridine adsorbed at a silver electrode[J].Chem Phys Lett,1974,26:163-166. [11]Jeanmaire D L,Van Duyne R P.Surface Raman spec-troelectrochemistry.Part I.Heterocyclic,aromatic,and aliphatic amines adsorbed on the anodized silver elec-trode[J].J Electroanal Chem,1977,84:1-17. [12]Zhao L L,Jensen L,Schatz G C.Pyridine-Ag-20clus-ter:A model system for studying surface-enhanced Ra-man scattering[J].J Am Chem Soc,2006,128:2911-2919. [13]Angel S M,Katz I F,Archbald D D,et al.Near-infrared surface-enhanced Raman spectroscopy.Part I:Copper and gold electrodes[J].Appl Spectrosc,1988,42:1327-1331. [14]Gao J S,Tian Z Q.Surface enhanced Raman scattering of pyridine at copper electrodes excited with a514.5nm line[J].Chem Phys Lett,1996,262:151-154. [15]Wilson E B.The normal modes and frequencies of vi-bration of the regular plane hexagon model of the ben-zene molecule[J].Physical Review,1934,45:706-714. [16]Wu D Y,Ren B,Jiang Y X,et al.Density functional study and normal-mode analysis of the bindings and vibrational frequency shifts of the pyridine-M(M=Cu,Ag,Au,Cu+,Ag+,Au+,and Pt)complexes[J].J Phys Chem A,2002,106:9042-9052. [17]Klots T D.Raman vapor spectrum and vibrational as-signment for pyridine[J].Spectrochim Acta Part A,1998,54:1481-1498. [18]Urena F P,Gomez M F,Gonzalez J J L,et al.A new in-sight into the vibrational analysis of pyridine[J].Spectrochim Acta,Part A,2003,59:2815-2839. [19]Wu D Y,Hayashi M,Lin S H,et al.Theoretical differ-ential Raman scattering cross-sections of totally-sym-metric vibrational modes of free pyridine and pyridine-metal cluster complexes[J].Spectrochim Acta Part A,2004,60:137-146. [20]Nakai H,Nakatsuji H.Electronic mechanism of thesurface enhanced Raman scattering[J].J Chem Phys,1995,103:2286-2294. [21]Wu D Y,Hayashi M,Chang C H,et al.Bonding inter-action,low-lying states and excited charge-transfer states of pyridine-metal clusters:Pyridine-Mn(M=Cu,Ag,Au;n=2-4)[J].J Chem Phys,2003,118:4073-4085. [22]Wu D Y,Hayashi M,Shiu Y J,et al.A quantum chem-ical study of bonding interaction,vibrational frequen-cies,force constants,and vibrational coupling of pyri-dine-Mn(M=Cu,Ag,Au;n=2-4)[J].J Phys Chem A,2003,107:9658-9667. [23]Wu D Y,Ren B,Xu X,et al.Periodic trends in the bonding and vibrational coupling:Pyridine interacting with transition metals and noble metals studied by sur-face-enhanced Raman spectroscopy and density-func-tional theory[J].J Chem Phys,2003,119:1701-1709. [24]Wu D Y,Ren B,Tian Z Q.A theoretical study on SERS intensity of pyridine adsorbed on transition metal electrodes[J].Isr J Chem,2006,46:317-327. [25]Wu D Y,Liu X M,Duan S,et al.Chemical enhance-ment effects in SERS spectra:A quantum chemical study of pyridine interacting with copper,silver,gold and platinum metals[J].J Phys Chem C,2008,112:4195-4204. [26]Wu D Y,Duan S,Ren B,et al.Density functional theo-ry study of surface-enhanced Raman scattering spectra of pyridine adsorbed on noble and transition metal sur-faces[J].J Raman Spectrosc,2005,36:533-540. [27]Wu D Y,Ren B,Tian Z Q.Binding interactions and Raman spectral properties of pyridine interacting with bimetallic silver-gold clusters[J].Chem Phys Chem,2006,7:619-628. [28]Xie Y,Wu D Y,Liu G K,et al.Adsorption and photon-driven charge transfer of pyridine on a cobalt electrode analyzed by surface enhanced Raman spectroscopy and relevant theories[J].J Electroanal Chem,2003,(554/555):417-425. [29]Lee M T,Wu D Y,Tian Z Q,et al.Effect of displace-ment and distortion of potential energy surfaces and o-verlapping resonances of electronic transitions on sur-face-enhanced Raman scattering:Models and ab initio theoretical calculation[J].J Chem Phys,2005,122:094719. [30]Ding Song-yuan(丁松园),Wu De-yin(吴德印),Yang Zhi-lin(杨志林),et al.Some progresses in chemical enhancement mechanism of surface-enhanced Raman scattering[J].Chemical Journal of Chinese U-niversities(高等化学学报),2008,29:2569-2581. [31]Bandy B J,Lloyd D R,Richardson N V.Selection rules in photoemission from adsorbates:Pyridine adsorbed on copper[J].Surf Sci,1979,89:344-353. [32]Frank K H,Dudde R,Koch E E.Electron affinity levels of benzene and azabenzenes on Cu(111)and Au(110)revealed by inverse photoemission[J].Chem Phys Lett,1986,132:83-87. [33]Golab J T,Sprague J R,Carron K T,et al.A surface enhanced hyper-Raman scattering study of pyridine adsorbed onto silver:Experiment and theory[J].J Chem Phys,1988,88:7942-7981. [34]Demuth J E,Christmann K,Sanda P N.The vibrations and structure of pyridine chemisorbed on Ag(111):the occurrence of a compressional phase transformation[J].Chem Phys Lett,1980,76:201-206. [35]Cai W B,Wan L J,Noda H,et al.Orientational phase transition in a pyridine adlayer on gold(111)in aque-ous solution studied by in situ Infrared spectroscopy and scanning tunneling microscopy[J].Langmuir,1998,14:6992-6998. [36]Haq S,King D A.Configurational transitions of benzene and pyridine adsorbed on Pt｛111｝and Cu｛110｝sur-faces:An infrared study[J].J Phys Chem,1996,100:16957-16965. [37]Zuo C,Jagodzinski P W.Surface-enhanced Raman scattering of pyridine using different metals:Differ-ences and explanation based on the selective formation ofα-pyridyl on metal surfaces[J].J Phys Chem B,2005,109:1788-1793. [38]Huo S-J,Xue X-K,Yan,et al.Extending in situ Atten-uated-total-reflection surface-enhanced infrared ab-sorption spectroscopy to Ni Electrodes[J].J Phys Chem B,2006,110:4162-4169. [39]Lee C,Yang W,Parr R G.Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density[J].Phys Rev B,1988,37:785-789. [40]Becke A D.Density-functional thermochemistry.III.The role of exact exchange[J].J Chem Phys,1993,98:5648-5652. [41]Hay P J,Wadt W R.Ab initio effective core potentials for molecular calculations.Potentials for the transition metal atoms scandium to mercury[J].J Chem Phys,1985,82:270-283. [42]Wadt W R,Hay P J.Ab initio effective core potentials for molecular calculations.Potentials for main group elements sodium to bismuth[J].J Chem Phys,1985,82:284-298. [43]Krishnan R,Binkley J S,Seeger R,et al.elf-consistentmolecular orbital methods.XX.A basis set for corre-lated wave functions[J].J Chem Phys,1980,72:650-654. [44]McLean A D,Chandler G S.Contracted Gaussian basis sets for molecular calculations.I.Second row atoms,Z=11-18[J].J Chem Phys,1980,72:5639-5648. [45]Neugebauer J,Reiher M,Kind C,et al.Quantum chem-ical calculation of vibrational spectra of large mole-cules-Raman and IR spectra for buckminsterfullerene[J].J Comput Chem,2002,23:895-910. [46]Bauernschmitt R,Ahlrichs R.Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory[J].Chem Phys Lett,1996,256:454-464. [47]Dykstra C E,Jasien P G.Derivative Hartree-Fock theo-ry to all orders[J].Chem Phys Lett,1984,109:388-393. [48]Lee J G,Ahner J,Yates J J T.The adsorption confor-mation of chemisorbed pyridine on the Cu(110)sur-face[J].J Chem Phys,2001,114:1414-1419. [49]Yang M C,Rockey T J,Pursell D,et al.Layer-by-layer structure in ultrathin aniline and pyridine films on Ag(111)[J].J Phys Chem B,2001,105:11945-11948. [50]Bilic A,Reimers J R,Hush N S.Adsorption of pyridine on the gold(111)surface:Implications for"alligator clips"for molecular wires[J].J Phys Chem B,2002,106:6740-6747. [51]Lombardi J L,Knight E A S,Birke R L.Evidence for a silver adatom-molecule complex in surface-enhanced Raman scattering[J].Chem Phys Lett,1981,79:214-218. [52]Creighton J A,Alvarez M S,Weltz D A,et al.Surface-enhanced Raman scattering by molecules adsorbed on aqueous copper colloids[J].J Phys Chem.1983,87:4793-4799. [53]Creighton J A,Nltachford C G,Albrecht M G.Plasma resonance enhancement of Raman scattering by pyri-dine adsorbed on silver or gold sol particles of size comparable to the excitation wavelength[J].J Chem Soc,Faraday Trans2,1979,75:790-798. [54]Yamada H,Nagata H,Toba K,et al.Charge transfer band and SERS mechanism for the pyridine-Ag system[J].Surf Sci,1987,182:269-286. [55]Persson B N J.On the theory of surface-enhanced Ra-man scattering[J].Chem Phys Lett,1981,82:561-565. [56]Otto A,Billman J,Eickmans J,et al.The"adatom model"of SERS(surface enhanced Raman scatter-ing):the present status[J].Surf Sci,1984,138:319-318. [57]Bryant M A,loa S L,Pemberton J E.Raman scattering from monolayer films of thiophenol and4-mercaptopyr-idine at platinum surfaces[J].Langmuir,1992,8:753-756.