Size-dependence of the enhanced Raman scattering of pyridine adsorbed on Agn (n = 2-8, 20) clusters

We present a time-dependent density functional theory (TDDFT) study of the size-dependence of the absorption and Raman scattering properties of pyridine interacting with small silver nanoclusters Agn (n = 2−8, 20). By employing a recently developed short-time approximation for the Raman scattering cross section we simulate both the normal and the “surface”-enhanced Raman spectra. The absorption spectra of the small silver clusters are studied both in the gas phase and embedded in rare gas matrices. We find that both the absorption and Raman properties depend strongly on cluster size and adsorption site. The normal Raman spectra of Agn−pyridine complexes resemble that of isolated pyridine, with enhancements which increase as cluster size increases. In contrast to this, both the enhancement and the appearance of the “surface”-enhanced Raman spectrum show a very strong dependence on cluster size. The total enhancements for the complexes are between 103 and 104 and quite surprisingly the strongest enhancement...

[1]  K. Jackson,et al.  First-principles study of intermediate size silver clusters: Shape evolution and its impact on cluster properties. , 2006, The Journal of chemical physics.

[2]  W. Ho,et al.  Imaging and vibrational spectroscopy of single pyridine molecules on Ag(110) using a low-temperature scanning tunneling microscope. , 2006, The Journal of chemical physics.

[3]  G. Schatz,et al.  Surface-enhanced raman scattering of pyrazine at the junction between two Ag20 nanoclusters. , 2006, Nano letters.

[4]  George C Schatz,et al.  Resonance Raman scattering of rhodamine 6G as calculated using time-dependent density functional theory. , 2006, The journal of physical chemistry. A.

[5]  G. Schatz,et al.  Pyridine-Ag20 cluster: a model system for studying surface-enhanced Raman scattering. , 2006, Journal of the American Chemical Society.

[6]  G. Schatz,et al.  Theory and method for calculating resonance Raman scattering from resonance polarizability derivatives. , 2005, The Journal of chemical physics.

[7]  S. Ogut,et al.  Size dependence of the static polarizabilities and absorption spectra of Agn (n=2-8) clusters , 2005 .

[8]  J. Tomasi,et al.  Quantum mechanical continuum solvation models. , 2005, Chemical reviews.

[9]  L Jensen,et al.  Finite lifetime effects on the polarizability within time-dependent density-functional theory. , 2005, The Journal of chemical physics.

[10]  R. Dickson,et al.  Nanoparticle-free single molecule anti-stokes Raman spectroscopy. , 2005, Physical review letters.

[11]  P. Johansson.  Illustrative direct ab initio calculations of surface Raman spectra. , 2005, Physical chemistry chemical physics : PCCP.

[12]  E. Jacquet,et al.  Spectroscopic properties of Na clusters embedded in a rare-gas matrix (4 pages) , 2005 .

[13]  J. Soler,et al.  Trends in the structure and bonding of noble metal clusters , 2004 .

[14]  W. P. Hall,et al.  A Localized Surface Plasmon Resonance Biosensor: First Steps toward an Assay for Alzheimer's Disease , 2004 .

[15]  S. Lin,et al.  Theoretical differential Raman scattering cross-sections of totally-symmetric vibrational modes of free pyridine and pyridine-metal cluster complexes. , 2004, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[16]  R. V. Van Duyne,et al.  A glucose biosensor based on surface-enhanced Raman scattering: improved partition layer, temporal stability, reversibility, and resistance to serum protein interference. , 2004, Analytical chemistry.

[17]  Stephan Link,et al.  Optical properties and ultrafast dynamics of metallic nanocrystals. , 2003, Annual review of physical chemistry.

[18]  John R. Lombardi,et al.  Ab Initio Frequency Calculations of Pyridine Adsorbed on an Adatom Model of a SERS Active Site of a Silver Surface , 2003 .

[19]  Markus Reiher,et al.  Quantum chemical calculation of vibrational spectra of large molecules—Raman and IR spectra for Buckminsterfullerene , 2002, J. Comput. Chem..

[20]  G. Cardini,et al.  Density Functional Study on the Adsorption of Pyrazole onto Silver Colloidal Particles , 2002 .

[21]  M. Wolf,et al.  Two-photon photoemission spectroscopy of pyridine adsorbed on Cu(111) , 2002 .

[22]  T. Rockey,et al.  Layer-by-Layer Structure in Ultrathin Aniline and Pyridine Films on Ag(111) , 2001 .

[23]  F. Matthias Bickelhaupt,et al.  Chemistry with ADF , 2001, J. Comput. Chem..

[24]  G. Ertl,et al.  Ag8 fluorescence in argon. , 2001, Physical review letters.

[25]  A. Otto,et al.  Search for dynamical charge transfer excitations of CO and pyridine on copper by EELS , 2001 .

[26]  J. Yates,et al.  The adsorption conformation of chemisorbed pyridine on the Cu(110) surface , 2001 .

[27]  M. Halls,et al.  Surface-Enhanced Raman Spectra of Phthalimide. Interpretation of the SERS Spectra of the Surface Complex Formed on Silver Islands and Colloids , 2000 .

[28]  Hongxing Xu,et al.  Spectroscopy of Single Hemoglobin Molecules by Surface Enhanced Raman Scattering , 1999 .

[29]  G. Ertl,et al.  Fluorescence and excitation spectra of Ag4 in an argon matrix , 1999 .

[30]  M. Moskovits,et al.  Tricapped tetrahedral Ag7: A structural determination by resonance Raman spectroscopy and density functional theory , 1999 .

[31]  Louis E. Brus,et al.  Surface Enhanced Raman Spectroscopy of Individual Rhodamine 6G Molecules on Large Ag Nanocrystals , 1999 .

[32]  M. Moskovits,et al.  RESONANCE RAMAN SPECTROSCOPY OF MATRIX-ISOLATED MASS-SELECTED FE3 AND AG3 , 1999 .

[33]  R. Dasari,et al.  Ultrasensitive chemical analysis by Raman spectroscopy. , 1999, Chemical reviews.

[34]  Tom Ziegler,et al.  An implementation of the conductor-like screening model of solvation within the Amsterdam density functional package , 1999 .

[35]  G. Bertsch,et al.  Optical response of small silver clusters , 1999, physics/9903041.

[36]  J. Pittner,et al.  An accurate relativistic effective core potential for excited states of Ag atom: An application for studying the absorption spectra of Agn and Agn+ clusters , 1999 .

[37]  A. Campion,et al.  Surface-enhanced Raman scattering , 1998 .

[38]  T. Klots.  Raman vapor spectrum and vibrational assignment for pyridine 1 Contribution number 370 from the Bart , 1998 .

[39]  G. Ertl,et al.  Light emission during the agglomeration of silver clusters in noble gas matrices , 1998 .

[40]  M. Moskovits,et al.  Ag5 is a planar trapezoidal molecule , 1998 .

[41]  A. Myers.  Molecular electronic spectral broadening in liquids and glasses. , 1998, Annual review of physical chemistry.

[42]  R. Dasari,et al.  Single Molecule Detection Using Surface-Enhanced Raman Scattering (SERS) , 1997 .

[43]  Steven R. Emory,et al.  Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering , 1997, Science.

[44]  G. Ertl,et al.  Chemiluminescence in the Agglomeration of Metal Clusters , 1996, Science.

[45]  J. Storhoff,et al.  A DNA-based method for rationally assembling nanoparticles into macroscopic materials , 1996, Nature.

[46]  Evert Jan Baerends,et al.  Relativistic total energy using regular approximations , 1994 .

[47]  J. Buttet,et al.  Optical response of Ag2, Ag3, Au2, and Au3 in argon matrices , 1993 .

[48]  Liebsch.  Surface-plasmon dispersion and size dependence of Mie resonance: Silver versus simple metals. , 1993, Physical review. B, Condensed matter.

[49]  Evert Jan Baerends,et al.  Relativistic regular two‐component Hamiltonians , 1993 .

[50]  Walt A. de Heer,et al.  The physics of simple metal clusters: experimental aspects and simple models , 1993 .

[51]  Matthias Brack,et al.  The physics of simple metal clusters: self-consistent jellium model and semiclassical approaches , 1993 .

[52]  Fedrigo,et al.  Collective dipole oscillations in small silver clusters embedded in rare-gas matrices. , 1993, Physical review. B, Condensed matter.

[53]  A. Klamt,et al.  COSMO : a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient , 1993 .

[54]  G. Schatz,et al.  Ab initio and semiempirical molecular orbital studies of surface enhanced and bulk hyper‐Raman scattering from pyridine , 1992 .

[55]  Piercarlo Fantucci,et al.  Quantum Chemistry of Small Clusters of Elements of Groups Ia, Ib, and IIa: Fundamental Concepts, Predictions, and Interpretation of Experiments , 1991 .

[56]  J. Rivoal,et al.  Deposition of mass selected silver clusters in rare gas matrices , 1990 .

[57]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[58]  George C. Schatz,et al.  A surface enhanced hyper‐Raman scattering study of pyridine adsorbed onto silver: Experiment and theory , 1988 .

[59]  K. J. Maynard,et al.  Surface Raman spectroscopy of a number of cyclic aromatic molecules adsorbed on silver: selection rules and molecular reorientation , 1988 .

[60]  W. Halperin,et al.  Quantum size effects in metal particles , 1986 .

[61]  S. Mukamel,et al.  Raman excitation profiles of polyatomic molecules in condensed phases. A stochastic theory , 1986 .

[62]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[63]  Frank,et al.  Orientational phase transition in the system pyridine/Ag(111): A near-edge x-ray-absorption fine-structure study. , 1986, Physical review letters.

[64]  A. Otto,et al.  Inverse photoemission of pyridine on silver (111) , 1985 .

[65]  M. Moskovits.  Surface-enhanced spectroscopy , 1985 .

[66]  D. M. Wood,et al.  Quantum size effects in the optical properties of small metallic particles , 1982 .

[67]  P. S. Bechthold,et al.  Luminescence and enhanced raman spectra of pure and pyridine-bonded small silver clusters , 1982 .

[68]  P. Avouris,et al.  Electronic excitations of benzene, pyridine, and pyrazine adsorbed on Ag(111) , 1981 .

[69]  P. Sanda,et al.  The vibrations and structure of pyridine chemisorbed on Ag(111): the occurrence of a compressional phase transformation , 1980 .

[70]  R. Hester,et al.  The dependence of the intensity of Raman bands of pyridine at a silver electrode on the wavelength of excitation , 1978 .

[71]  D. L. Jeanmaire,et al.  Surface raman spectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode , 1977 .

[72]  R. Clark,et al.  The Far-Infrared Spectra of Metal-Halide Complexes of Pyridine and Related Ligands , 1965 .