Nonresonant hyper-Raman and hyper-Rayleigh scattering in benzene and pyridine

Neddersen, John P.; Mounter, Sarah A.; Bostick, J. M.; Johnson, Carey K.

doi:10.1063/1.456592

Cited by 40 publications

(21 citation statements)

References 35 publications

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“…We show that the asymptotically correct statistical average of orbital potential ͑SAOP͒ model potential combined with a quadruple zeta polarized basis set can be used to obtain a hyper-Raman spectrum for pyridine and pyridine/Ag 20 that agrees with the experimental results reported by Golab et al 2 and Neddersen et al 41 Although ADF does not currently allow the calculation of hyperpolarizabilities near or at resonance, the hyper-Raman enhance-ment that we have determined provides a good estimate of the chemical effects in SEHRS, and with this we will revisit the earlier conclusions concerning the relative importance of the chemical and electromagnetic contributions to the enhancement factor. Calculating hyperpolarizability derivatives is less established in literature than polarizability derivatives, although codes exist with such functionality in the static limit.…”

Section: Introductionsupporting

confidence: 85%

Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

Valley

Jensen

Autschbach

et al. 2010

The Journal of Chemical Physics

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Articles you may be interested inTheoretical approach for optical response in electrochemical systems: Application to electrode potential dependence of surface-enhanced Raman scattering Quantitative evaluation of blinking in surface enhanced resonance Raman scattering and fluorescence by electromagnetic mechanism J. Chem. Phys. 136, 024703 (2012); 10.1063/1.3675567Photon-driven charge transfer and Herzberg-Teller vibronic coupling mechanism in surface-enhanced Raman scattering of p-aminothiophenol adsorbed on coinage metal surfaces: A density functional theory study J. Chem. Phys. 135, 134707 (2011); 10.1063/1.3643766Studies on adsorption of mono-and multi-chromophoric hemicyanine dyes on silver nanoparticles by surfaceenhanced resonance raman and theoretical calculations Hyper-Raman spectra for pyridine and pyridine on the surface of a tetrahedral 20 silver atom cluster are calculated using static hyperpolarizability derivatives obtained from time dependent density functional theory. The stability of the results with respect to choice of exchange-correlation functional and basis set is verified by comparison with experiment and with Raman spectra calculated for the same systems using the same methods. Calculated Raman spectra were found to match well with experiment and previous theoretical calculations. The calculated normal and surface enhanced hyper-Raman spectra closely match experimental results. The chemical enhancement factors for hyper-Raman are generally larger than for Raman ͑10 2 −10 4 versus 10 1 −10 2 ͒. Integrated hyper-Raman chemical enhancement factors are presented for a set of substituted pyridines. A two-state model is developed to predict these chemical enhancement factors and this was found to work well for the majority of the molecules considered, providing a rationalization for the difference between hyper-Raman and Raman enhancement factors.

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Section: Introductionsupporting

confidence: 85%

Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

Valley

Jensen

Autschbach

et al. 2010

The Journal of Chemical Physics

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“…The stick spectrum (note: it has been scaled) obtained from calculation of intensities at each normal-mode frequency is overlaid by the spectrum where each peak has been convoluted with a Lorentzian with a width of 20 cm −1 . Peaks and intensities seen in the experimental spectrum 48,49 are reproduced well by the calculations. The minor Adding a tetrahedral 20-silver-atom cluster allows the investigation of phenomena such as the chemical enhancements observed in SERS.…”

Section: Example 1: Raman Spectra Of Pyridine and Pyridine On A Silvesupporting

confidence: 66%

“…Luckily, for pyridine there are experimental measurements, which are matched rather well by the calculated spectrum. 49 Not all the peaks calculated can be verified due to noise in the experiment, but the relative intensities of those that are observed matches well. …”

Section: Example 1: Raman Spectra Of Pyridine and Pyridine On A Silvementioning

confidence: 70%

Calculating the Raman and HyperRaman Spectra of Large Molecules and Molecules Interacting with Nanoparticles

Valley¹,

Jensen

Autschbach

et al. 2011

Computational Methods for Large Systems

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This chapter describes calculations of the Raman and hyperRaman spectra of large molecules and molecules interacting with nanoparticles using time-dependent density functional theory with the Amsterdam density functional (ADF) program package. The ADF code uses Slater basis functions, which provides a very efficient basis set for optical property calculations using density functional theory (DFT). In addition, ADF has special capabilities for determining resonant Raman spectra, which is enabled by the inclusion of excited-state lifetimes in the calculations, and therefore polarizabilities and polarizability derivatives for wavelengths close to resonance can be determined. Specific details of the theory are described, and examples of applications to pyridine (for nonresonant properties) and uracil (for resonant properties) are provided.

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“…42 To the best of our knowledge, this is the first time the SEHRS spectrum of benzene has been obtained, although a non-resonant hyper-Raman spectrum has been obtained previously in which only one band at 668 cm 1 (A 2u , 11 ) was observed. 27 Three bands were clearly observed in the SERS spectra of benzene: at 980 cm 1 ( 1, A 1g ), 1173 cm 1 ( 9a/9b, E 2g ) and 1595 cm 1 ( 8a/8b, E 2g ), respectively. Compared with the normal Raman spectrum, the wavenumbers of the Figure 16.…”

Section: Comparison Between the Observed And Calculated Infrared Rammentioning

confidence: 97%

“…To the best of our knowledge there has been no report on the SEHRS study of benzene. Normal hyper-Raman spectra of pyridine and benzene have been reported by Acker et al, 26 and Heddersen et al, 27 respectively.…”

Section: Introductionmentioning

confidence: 99%

Surface‐enhanced hyper‐Raman and surface‐enhanced Raman scattering from molecules adsorbed on nanoparticles‐on‐smooth‐electrode (NOSE) substrate I. Pyridine, pyrazine and benzene

Huang

Петров

et al. 2005

J Raman Spectroscopy

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Metal nanoparticles-on-smooth-electrode (NOSE) was used as the substrate in a potential-dependent surface-enhanced hyper-Raman(SEHRS), hyper-Rayleigh(SEHRyS) and Raman (SERS) study of adsorbed molecules of pyridine, pyrazine and benzene. The three molecules are chosen because they are known to adsorb in different orientations on an Ag surface, thus allowing us to examine the sensitivity of SEHRS and SERS signals to the orientation of adsorbed molecules on the NOSE substrate. A computational subroutine is developed and interfaced with Gaussian-98 to calculate the numeric infrared, Raman and hyper-Raman intensities, as well as their projections along any molecular-fixed orientation axis at the level of finite perturbation theory. In this study, we tried to make four types of systematic comparisons. First, we compared the performance of Ag n jAg NOSE substrate with that of traditional substrates such as a randomly roughened Ag electrode or a randomly aggregated Ag sol in SEHRS and SERS. Secondly, we tried to compare between infrared, Raman and hyper-Raman spectra, which represent the parity-differentiated one-photon, two-photon and three-photon processes, respectively, with the aim of examining the complementarity between SEHRS and SERS as well as between SEHRS and infrared absorption. Thirdly, we compared isotropic normal spectra with surface-enhanced spectra (SEHRS and SERS), with the aim of examining the effect of surface adsorption on the selectivity and enhancement. Lastly, we made a systematic comparison between the observed and calculated spectra for both isotropic and surface spectra, which allowed us to assign and interpret the observed data and to infer the most likely orientation of the adsorbed molecules. The NOSE method can be generalized easily to other metal nanoparticles dispersed on a smooth inert metal electrode. The rapid development in the synthesis of metal nanoparticles of various sizes, shapes and crystalline states makes the NOSE method a much more flexible and versatile substrate in the study and applications of SERS and SEHRS techniques.

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Nonresonant hyper-Raman and hyper-Rayleigh scattering in benzene and pyridine

Cited by 40 publications

References 35 publications

Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

Calculating the Raman and HyperRaman Spectra of Large Molecules and Molecules Interacting with Nanoparticles

Surface‐enhanced hyper‐Raman and surface‐enhanced Raman scattering from molecules adsorbed on nanoparticles‐on‐smooth‐electrode (NOSE) substrate I. Pyridine, pyrazine and benzene

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