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Dive into the research topics where Jon P. Camden is active.

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Featured researches published by Jon P. Camden.


Journal of the American Chemical Society | 2008

Probing the structure of single-molecule surface-enhanced Raman scattering hot spots.

Jon P. Camden; Jon A. Dieringer; Yingmin Wang; David J. Masiello; Lawrence D. Marks; George C. Schatz; Richard P. Van Duyne

We present here a detailed study of the specific nanoparticle structures that give rise to single-molecule surface-enhanced Raman scattering (SMSERS). A variety of structures are observed, but the simplest are dimers of Ag nanocrystals. We chose one of these structures for detailed study using electrodynamics calculations and found that the electromagnetic SERS enhancement factors of 10(9) are easily obtained and are consistent with single-molecule SERS activity.


Accounts of Chemical Research | 2008

Controlled Plasmonic Nanostructures for Surface-Enhanced Spectroscopy and Sensing

Jon P. Camden; Jon A. Dieringer; Jing Zhao; Richard P. Van Duyne

After its discovery more than 30 years ago, surface-enhanced Raman spectroscopy (SERS) was expected to have major impact as a sensitive analytical technique and tool for fundamental studies of surface species. Unfortunately, the lack of reliable and reproducible fabrication methods limited its applicability. In recent years, SERS has enjoyed a renaissance, and there is renewed interest in both the fundamentals and applications of SERS. New techniques for nanofabrication, the design of substrates that maximize the electromagnetic enhancement, and the discovery of single-molecule SERS are driving the resurgence of this field. This Account highlights our groups recent work on SERS. Initially, we discuss SERS substrates that have shown proven reproducibility, stability, and large field enhancement. These substrates enable many analytical applications, such as anthrax detection, chemical warfare agent stimulant detection, and in vitro and in vivo glucose sensing. We then turn to a detailed study of the wavelength and distance dependence of SERS, which further illustrate predictions obtained from the electromagnetic enhancement mechanism. Last, an isotopic labeling technique applied to the rhodamine 6G (R6G)/silver system serves as an additional proof of the existence of single-molecule SERS and explores the dynamical features of this process. This work, in conjunction with theoretical calculations, allows us to comment on the possible role of charge transfer in the R6G/silver system.


Journal of the American Chemical Society | 2009

Surface-Enhanced Raman Excitation Spectroscopy of a Single Rhodamine 6G Molecule

Jon A. Dieringer; Kristin L. Wustholz; David J. Masiello; Jon P. Camden; Samuel L. Kleinman; George C. Schatz; Richard P. Van Duyne

The surface-enhanced Raman excitation profiles (REPs) of rhodamine 6G (R6G) on Ag surfaces are studied using a tunable optical parametric oscillator excitation source and versatile detection scheme. These experiments afford the ability to finely tune the excitation wavelength near the molecular resonance of R6G (i.e., approximately 500-575 nm) and perform wavelength-scanned surface-enhanced Raman excitation measurements of a single molecule. The ensemble-averaged surface-enhanced REPs are measured for collections of molecules on Ag island films. The relative contributions of the 0-0 and 0-1 vibronic transitions to the surface-enhanced REPs vary with vibrational frequency. These results highlight the role of excitation energy in determining the resonance Raman intensities for R6G on surface-enhancing nanostructures. Single-molecule measurements are obtained from individual molecules of R6G on Ag colloidal aggregates, where single-molecule junctions are located using the isotope-edited approach. Overall, single-molecule surface-enhanced REPs are narrow in comparison to the ensemble-averaged excitation profiles due to a reduction in inhomogeneous broadening. This work describes the first Raman excitation spectroscopy studies of a single molecule, revealing new information previously obscured by the ensemble.


Journal of Physical Chemistry A | 2009

Surface-enhanced Raman spectroscopy of benzenethiol adsorbed from the gas phase onto silver film over nanosphere surfaces: determination of the sticking probability and detection limit time.

Kevin B. Biggs; Jon P. Camden; Jeffrey N. Anker; Richard P. Van Duyne

A chemical warfare agent (CWA) gas detector based on surface-enhanced Raman spectroscopy (SERS) using robust nanostructured substrates and a portable Raman spectrometer is a promising alternative to existing modalities. A gas-dosing apparatus was constructed to simulate chemical gas exposure and provide a platform for quantitative analysis of SERS detection. As a first step toward characterizing SERS detection from the gas phase, benzenethiol (BT) has been chosen as the test analyte. SERS spectra were monitored during BT adsorption onto a silver film over a nanosphere (AgFON) substrate. The SERS detection limit time (DLt) for BT on a AgFON at 356 K is found to be 6 ppm-s (30 mg-s m(-3)) for a data acquisition time (t(acq)) of 1 s. The DLt for this kinetically controlled sensor is fundamentally determined by the low sticking probability of BT on AgFONs which is determined to be approximately 2 x 10(-5) at 356 K. The sticking probability increases with increasing temperature consistent with an adsorption activation barrier of approximately 13 kJ mol(-1). Although the DLts found in the present study for BT are in the low ppm-s, a theoretical model of SERS detection indicates DLts below 1 ppb s(-1) for t(acq)= 1 s are, in fact, achievable using existing portable Raman instrumentation and AgFON surfaces. Achieving this goal requires the sticking probability be increased 3 orders of magnitude, illuminating the importance of appropriate surface functionalization.


Nano Letters | 2011

Correlated optical measurements and plasmon mapping of silver nanorods.

Beth S. Guiton; Vighter Iberi; Shuzhou Li; Donovan N. Leonard; Chad M. Parish; Paul Gabriel Kotula; M. Varela; George C. Schatz; Stephen J. Pennycook; Jon P. Camden

Plasmonics is a rapidly growing field, yet imaging of the plasmonic modes in complex nanoscale architectures is extremely challenging. Here we obtain spatial maps of the localized surface plasmon modes of high-aspect-ratio silver nanorods using electron energy loss spectroscopy (EELS) and correlate to optical data and classical electrodynamics calculations from the exact same particles. EELS mapping is thus demonstrated to be an invaluable technique for elucidating complex and overlapping plasmon modes.


Journal of Chemical Physics | 2004

Comparing the dynamical effects of symmetric and antisymmetric stretch excitation of methane in the Cl+CH4 reaction

Hans A. Bechtel; Jon P. Camden; Davida J. Ankeny Brown; Richard N. Zare

The effects of two nearly isoenergetic C-H stretching motions on the gas-phase reaction of atomic chlorine with methane are examined. First, a 1:4:9 mixture of Cl(2), CH(4), and He is coexpanded into a vacuum chamber. Then, either the antisymmetric stretch (nu(3)=3019 cm(-1)) of CH(4) is prepared by direct infrared absorption or the infrared-inactive symmetric stretch (nu(1)=2917 cm(-1)) of CH(4) is prepared by stimulated Raman pumping. Photolysis of Cl(2) at 355 nm generates fast Cl atoms that initiate the reaction with a collision energy of 1290+/-175 cm(-1) (0.16+/-0.02 eV). Finally, the nascent HCl or CH(3) products are detected state-specifically via resonance enhanced multiphoton ionization and separated by mass in a time-of-flight spectrometer. We find that the rovibrational distributions and state-selected differential cross sections of the HCl and CH(3) products from the two vibrationally excited reactions are nearly indistinguishable. Although Yoon et al. [J. Chem. Phys. 119, 9568 (2003)] report that the reactivities of these two different types of vibrational excitation are quite different, the present results indicate that the reactions of symmetric-stretch excited or antisymmetric-stretch excited methane with atomic chlorine follow closely related product pathways. Approximately 37% of the reaction products are formed in HCl(v=1,J) states with little rotational excitation. At low J states these products are sharply forward scattered, but become almost equally forward and backward scattered at higher J states. The remaining reaction products are formed in HCl(v=0,J) and have more rotational excitation. The HCl(v=0,J) products are predominantly back and side scattered. Measurements of the CH(3) products indicate production of a non-negligible amount of umbrella bend excited methyl radicals primarily in coincidence with the HCl(v=0,J) products. The data are consistent with a model in which the impact parameter governs the scattering dynamics.


ACS Nano | 2012

Characterization of the electron- and photon-driven plasmonic excitations of metal nanorods.

Nicholas W. Bigelow; Alex Vaschillo; Vighter Iberi; Jon P. Camden; David J. Masiello

A computational analysis of the electron- and photon-driven surface-plasmon resonances of monomer and dimer metal nanorods is presented to elucidate the differences and similarities between the two excitation mechanisms in a system with well-understood optical properties. By correlating the nanostructures simulated electron energy-loss spectrum and loss-probability maps with its induced polarization and scattered electric field we discern how certain plasmon modes are selectively excited and how they funnel energy from the excitation source into the near- and far-field. Using a fully retarded electron-scattering theory capable of describing arbitrary three-dimensional nanoparticle geometries, aggregation schemes, and material compositions, we find that electron energy-loss spectroscopy (EELS) is able to indirectly probe the same electromagnetic hot spots that are generated by an optical excitation source. Comparison with recent experiment is made to verify our findings.


Journal of Chemical Physics | 2004

Bond and mode selectivity in the reaction of atomic chlorine with vibrationally excited CH2D2.

Hans A. Bechtel; Zee Hwan Kim; Jon P. Camden; Richard N. Zare

The title reaction is investigated by co-expanding a mixture of Cl2 and CH2D2 into a vacuum chamber and initiating the reaction by photolyzing Cl2 with linearly polarized 355 nm light. Excitation of the first C-H overtone of CH2D2 leads to a preference for hydrogen abstraction over deuterium abstraction by at least a factor of 20, whereas excitation of the first C-D overtone of CH2D2 reverses this preference by at least a factor of 10. Reactions with CH2D2 prepared in a local mode containing two quanta in one C-H oscillator /2000>- or in a local mode containing one quantum each in two C-H oscillators /1100> lead to products with significantly different rotational, vibrational, and angular distributions, although the vibrational energy for each mode is nearly identical. The Cl+CH2D2/2000>- reaction yields methyl radical products primarily in their ground state, whereas the Cl+CH2D2/1100> reaction yields methyl radical products that are C-H stretch excited. The HCl(v=1) rotational distribution from the Cl+CH2D2/2000>- reaction is significantly hotter than the HCl(v=1) rotational distribution from the Cl+CH2D2/1100> reaction, and the HCl(v=1) differential cross-section (DCS) of the Cl+CH2D2/2000>- reaction is more broadly side scattered than the HCl(v=1) DCS of the Cl+CH2D2/1100> reaction. The results can be explained by a simple spectator model and by noting that the /2000>- mode leads to a wider cone of acceptance for the reaction than the /1100> mode. These measurements represent the first example of mode selectivity observed in a differential cross section, and they demonstrate that vibrational excitation can be used to direct the reaction pathway of the Cl+CH2D2 reaction.


Journal of Chemical Physics | 2005

Effects of C-H stretch excitation on the H+CH4 reaction.

Jon P. Camden; Hans A. Bechtel; Davida J. Ankeny Brown; Richard N. Zare

We have investigated the effects of C-H stretching excitation on the H+CH4-->CH3+H2 reaction dynamics using the photo-LOC technique. The CH3 product vibrational state and angular distribution are measured for the reaction of fast H atoms with methane excited in either the antisymmetric stretching fundamental (nu3=1) or first overtone (nu3=2) with a center-of-mass collision energy of Ecoll ranging from 1.52 to 2.20 eV. We find that vibrational excitation of the nu3=1 mode enhances the overall reaction cross section by a factor of 3.0+/-1.5 for Ecoll=1.52 eV, and this enhancement factor is approximately constant over the 1.52-2.20-eV collision energy range. A local-mode description of the CH4 stretching vibration, in which the C-H oscillators are uncoupled, is used to describe the observed state distributions. In this model, the interaction of the incident H atom with either a stretched or an unstretched C-H oscillator determines the vibrational state of the CH3 product. We also compare these results to the similar quantities obtained previously for the Cl+CH4-->CH3+HCl reaction at Ecoll=0.16 eV [Z. H. Kim, H. A. Bechtel, and R. N. Zare, J. Chem. Phys. 117, 3232 (2002); H. A. Bechtel, J. P. Camden, D. J. A. Brown, and R. N. Zare, ibid. 120, 5096 (2004)] in an attempt to elucidate the differences in reactivity for the same initially prepared vibration.


Scientific Reports | 2013

Wafer-scale metasurface for total power absorption, local field enhancement and single molecule Raman spectroscopy

Dongxing Wang; Wenqi Zhu; Michael D. Best; Jon P. Camden; Kenneth B. Crozier

The ability to detect molecules at low concentrations is highly desired for applications that range from basic science to healthcare. Considerable interest also exists for ultrathin materials with high optical absorption, e.g. for microbolometers and thermal emitters. Metal nanostructures present opportunities to achieve both purposes. Metal nanoparticles can generate gigantic field enhancements, sufficient for the Raman spectroscopy of single molecules. Thin layers containing metal nanostructures (“metasurfaces”) can achieve near-total power absorption at visible and near-infrared wavelengths. Thus far, however, both aims (i.e. single molecule Raman and total power absorption) have only been achieved using metal nanostructures produced by techniques (high resolution lithography or colloidal synthesis) that are complex and/or difficult to implement over large areas. Here, we demonstrate a metasurface that achieves the near-perfect absorption of visible-wavelength light and enables the Raman spectroscopy of single molecules. Our metasurface is fabricated using thin film depositions, and is of unprecedented (wafer-scale) extent.

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Hans A. Bechtel

Lawrence Berkeley National Laboratory

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Guoliang Li

University of Tennessee

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Lasse Jensen

Pennsylvania State University

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Daniel W. Silverstein

Pennsylvania State University

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