Versatile silicon-waveguide supercontinuum for coherent mid-infrared spectroscopy

NASA Astrophysics Data System (ADS)

Nader, Nima; Maser, Daniel L.; Cruz, Flavio C.; Kowligy, Abijith; Timmers, Henry; Chiles, Jeff; Fredrick, Connor; Westly, Daron A.; Nam, Sae Woo; Mirin, Richard P.; Shainline, Jeffrey M.; Diddams, Scott

2018-03-01

Laser frequency combs, with their unique combination of precisely defined spectral lines and broad bandwidth, are a powerful tool for basic and applied spectroscopy. Here, we report offset-free, mid-infrared frequency combs and dual-comb spectroscopy through supercontinuum generation in silicon-on-sapphire waveguides. We leverage robust fabrication and geometrical dispersion engineering of nanophotonic waveguides for multi-band, coherent frequency combs spanning 70 THz in the mid-infrared (2.5 μm-6.2 μm). Precise waveguide fabrication provides significant spectral broadening with engineered spectra targeted at specific mid-infrared bands. We characterize the relative-intensity-noise of different bands and show that the measured levels do not pose any limitation for spectroscopy applications. Additionally, we use the fabricated photonic devices to demonstrate dual-comb spectroscopy of a carbonyl sulfide gas sample at 5 μm. This work forms the technological basis for applications such as point sensors for fundamental spectroscopy, atmospheric chemistry, trace and hazardous gas detection, and biological microscopy.

Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy

PubMed Central

Xiong, Wei; Laaser, Jennifer E.; Mehlenbacher, Randy D.; Zanni, Martin T.

2011-01-01

In the last ten years, two-dimensional infrared spectroscopy has become an important technique for studying molecular structures and dynamics. We report the implementation of heterodyne detected two-dimensional sum-frequency generation (HD 2D SFG) spectroscopy, which is the analog of 2D infrared (2D IR) spectroscopy, but is selective to noncentrosymmetric systems such as interfaces. We implement the technique using mid-IR pulse shaping, which enables rapid scanning, phase cycling, and automatic phasing. Absorptive spectra are obtained, that have the highest frequency resolution possible, from which we extract the rephasing and nonrephasing signals that are sometimes preferred. Using this technique, we measure the vibrational mode of CO adsorbed on a polycrystalline Pt surface. The 2D spectrum reveals a significant inhomogenous contribution to the spectral line shape, which is quantified by simulations. This observation indicates that the surface conformation and environment of CO molecules is more complicated than the simple “atop” configuration assumed in previous work. Our method can be straightforwardly incorporated into many existing SFG spectrometers. The technique enables one to quantify inhomogeneity, vibrational couplings, spectral diffusion, chemical exchange, and many other properties analogous to 2D IR spectroscopy, but specifically for interfaces. PMID:22143772

Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy.

PubMed

Xiong, Wei; Laaser, Jennifer E; Mehlenbacher, Randy D; Zanni, Martin T

2011-12-27

In the last ten years, two-dimensional infrared spectroscopy has become an important technique for studying molecular structures and dynamics. We report the implementation of heterodyne detected two-dimensional sum-frequency generation (HD 2D SFG) spectroscopy, which is the analog of 2D infrared (2D IR) spectroscopy, but is selective to noncentrosymmetric systems such as interfaces. We implement the technique using mid-IR pulse shaping, which enables rapid scanning, phase cycling, and automatic phasing. Absorptive spectra are obtained, that have the highest frequency resolution possible, from which we extract the rephasing and nonrephasing signals that are sometimes preferred. Using this technique, we measure the vibrational mode of CO adsorbed on a polycrystalline Pt surface. The 2D spectrum reveals a significant inhomogenous contribution to the spectral line shape, which is quantified by simulations. This observation indicates that the surface conformation and environment of CO molecules is more complicated than the simple "atop" configuration assumed in previous work. Our method can be straightforwardly incorporated into many existing SFG spectrometers. The technique enables one to quantify inhomogeneity, vibrational couplings, spectral diffusion, chemical exchange, and many other properties analogous to 2D IR spectroscopy, but specifically for interfaces.

High-power continuous-wave tunable 544- and 272-nm beams based on a diode-oscillator fiber-amplifier for calcium spectroscopy

NASA Astrophysics Data System (ADS)

Ko, Kwang-Hoon; Kim, Yonghee; Park, Hyunmin; Cha, Yong-Ho; Kim, Taek-Soo; Lee, Lim; Lim, Gwon; Han, Jaemin; Ko, Kwang-Hee; Jeong, Do-Young

2015-08-01

Continuous-wave single-frequency tunable 544- and 272-nm beams have been demonstrated by the second- and fourth-harmonic conversions of a 1088-nm fundamental beam from a diode-oscillator fiber-amplifier. The single-pass second-harmonic generation with a MgO-doped periodically poled stoichiometric LiTaO3 crystal and the external-cavity frequency-doubling technique with a bulk BBO crystal were employed to achieve an approximately 6-W 544-nm beam and a 1.5-W 272-nm beam, respectively. We characterized the second- and fourth-harmonic generations and discussed their applications to calcium spectroscopy.

Unified treatment and measurement of the spectral resolution and temporal effects in frequency-resolved sum-frequency generation vibrational spectroscopy (SFG-VS).

PubMed

Velarde, Luis; Wang, Hong-Fei

2013-12-14

The lack of understanding of the temporal effects and the restricted ability to control experimental conditions in order to obtain intrinsic spectral lineshapes in surface sum-frequency generation vibrational spectroscopy (SFG-VS) have limited its applications in surface and interfacial studies. The emergence of high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) with sub-wavenumber resolution [Velarde et al., J. Chem. Phys., 2011, 135, 241102] offers new opportunities for obtaining and understanding the spectral lineshapes and temporal effects in SFG-VS. Particularly, the high accuracy of the HR-BB-SFG-VS experimental lineshape provides detailed information on the complex coherent vibrational dynamics through direct spectral measurements. Here we present a unified formalism for the theoretical and experimental routes for obtaining an accurate lineshape of the SFG response. Then, we present a detailed analysis of a cholesterol monolayer at the air/water interface with higher and lower resolution SFG spectra along with their temporal response. With higher spectral resolution and accurate vibrational spectral lineshapes, it is shown that the parameters of the experimental SFG spectra can be used both to understand and to quantitatively reproduce the temporal effects in lower resolution SFG measurements. This perspective provides not only a unified picture but also a novel experimental approach to measuring and understanding the frequency-domain and time-domain SFG response of a complex molecular interface.

Enhanced detection of thiophenol adsorbed on gold nanoparticles by SFG and DFG nonlinear optical spectroscopy.

PubMed

Pluchery, Olivier; Humbert, Christophe; Valamanesh, Mehrnoush; Lacaze, Emmanuelle; Busson, Bertrand

2009-09-21

Sum frequency generation (SFG) and difference frequency generation (DFG) are applied to study vibrational resonance of the thiophenol molecule adsorbed on two different gold samples. One sample is made of 17 nm gold nanoparticles (AuNPs) fixed on a silicon substrate that has been previously functionalized with a silane monolayer (aminopropyltriethoxysilane, APTES). This sample is fully characterized through visible reflection spectroscopy and AFM. The second sample is a gold monocrystal also covered with thiophenol molecules. From their comparison, an enhancement factor of 21 is deduced for the SFG signal on AuNPs with respect to the Au(111), related to the surface plasmon resonance (SPR). From a combined analysis of the SFG and DFG spectra, we demonstrate that SFG/DFG spectroscopy is able to identify the nature of the substrate where the molecules are adsorbed. This opens new perspectives for this nonlinear spectroscopy by adding to its well-known intrinsic surface specificity, the ability to selectively probe the chemical layer capping the AuNPs.

Interferometric 2D Sum Frequency Generation Spectroscopy Reveals Structural Heterogeneity of Catalytic Monolayers on Transparent Materials.

PubMed

Vanselous, Heather; Stingel, Ashley M; Petersen, Poul B

2017-02-16

Molecular monolayers exhibit structural and dynamical properties that are different from their bulk counterparts due to their interaction with the substrate. Extracting these distinct properties is crucial for a better understanding of processes such as heterogeneous catalysis and interfacial charge transfer. Ultrafast nonlinear spectroscopic techniques such as 2D infrared (2D IR) spectroscopy are powerful tools for understanding molecular dynamics in complex bulk systems. Here, we build on technical advancements in 2D IR and heterodyne-detected sum frequency generation (SFG) spectroscopy to study a CO 2 reduction catalyst on nanostructured TiO 2 with interferometric 2D SFG spectroscopy. Our method combines phase-stable heterodyne detection employing an external local oscillator with a broad-band pump pulse pair to provide the first high spectral and temporal resolution 2D SFG spectra of a transparent material. We determine the overall molecular orientation of the catalyst and find that there is a static structural heterogeneity reflective of different local environments at the surface.

Terahertz transmission properties of silicon wafers using continuous-wave terahertz spectroscopy

NASA Astrophysics Data System (ADS)

Kim, Chihoon; Ahn, Jae Sung; Ji, Taeksoo; Eom, Joo Beom

2017-04-01

We present the spectral properties of Si wafers using continuous-wave terahertz (CW-THz) spectroscopy. By using a tunable laser source and a fixed distributed-feedback laser diode (DFB-LD), a stably tunable beat source for CW-THz spectroscopy system can be implemented. THz radiation is generated in the frequency range of 100 GHz-800 GHz by photomixing in a photoconductive antenna. We also measured CW-THz waveforms by changing the beat frequency and confirmed repeatability through repeated measurement. We calculated the peaks of the THz frequency by taking fast Fourier transforms (FFTs) of measured THz waveforms. The feasibility of CW-THz spectroscopy is demonstrated by the THz spectra of Si wafers with different resistivities, mobilities, and carrier concentrations. The results show that Si wafers with a lower resistivity absorb more THz waves. Thus, we expect our CW-THz system to have the advantage of being able to perform fast non-destructive analysis.

Thermally controlled comb generation and soliton modelocking in microresonators.

PubMed

Joshi, Chaitanya; Jang, Jae K; Luke, Kevin; Ji, Xingchen; Miller, Steven A; Klenner, Alexander; Okawachi, Yoshitomo; Lipson, Michal; Gaeta, Alexander L

2016-06-01

We report, to the best of our knowledge, the first demonstration of thermally controlled soliton mode-locked frequency comb generation in microresonators. By controlling the electric current through heaters integrated with silicon nitride microresonators, we demonstrate a systematic and repeatable pathway to single- and multi-soliton mode-locked states without adjusting the pump laser wavelength. Such an approach could greatly simplify the generation of mode-locked frequency combs and facilitate applications such as chip-based dual-comb spectroscopy.

Surface sum-frequency vibrational spectroscopy of nonpolar media

DOE PAGES

Sun, Shumei; Tian, Chuanshan; Shen, Y. Ron

2015-04-27

Sum-frequency generation spectroscopy is surface specific only if the bulk contribution to the signal is negligible. Negligible bulk contribution is, however, not necessarily true, even for media with inversion symmetry. The inevitable challenge is to find the surface spectrum in the presence of bulk contribution, part of which has been believed to be inseparable from the surface contribution. Here, we show that, for nonpolar media, it is possible to separately deduce surface and bulk spectra from combined phase-sensitive sum-frequency vibrational spectroscopic measurements in reflection and transmission. Finally, the study of benzene interfaces is presented as an example.

High resolution spectroscopy in the microwave and far infrared

NASA Technical Reports Server (NTRS)

Pickett, Herbert M.

1990-01-01

High resolution rotational spectroscopy has long been central to remote sensing techniques in atmospheric sciences and astronomy. As such, laboratory measurements must supply the required data to make direct interpretation of data for instruments which sense atmospheres using rotational spectra. Spectral measurements in the microwave and far infrared regions are also very powerful tools when combined with infrared measurements for characterizing the rotational structure of vibrational spectra. In the past decade new techniques were developed which have pushed high resolution spectroscopy into the wavelength region between 25 micrometers and 2 mm. Techniques to be described include: (1) harmonic generation of microwave sources, (2) infrared laser difference frequency generation, (3) laser sideband generation, and (4) ultrahigh resolution interferometers.

Salt Effects on Surface Structures of Polyelectrolyte Multilayers (PEMs) Investigated by Vibrational Sum Frequency Generation (SFG) Spectroscopy.

PubMed

Ge, Aimin; Matsusaki, Michiya; Qiao, Lin; Akashi, Mitsuru; Ye, Shen

2016-04-26

Sum frequency generation (SFG) vibrational spectroscopy was employed to investigate the surface structures of polyelectrolyte multilayers (PEMs) constructed by sequentially alternating adsorption of poly(diallyldimethylammonium chloride) (PDDA) and poly(styrenesulfonate) (PSS). It was found that the surface structures and surface charge density of the as-deposited PEMs of PDDA/PSS significantly depend on the concentration of sodium chloride (NaCl) present in the polyelectrolyte solutions. Furthermore, it was found that the surface structure of the as-deposited PEMs is in a metastable state and will reach the equilibrium state by diffusion of the polyelectrolyte chain after an aging process, resulting in a polyelectrolyte mixture on the PEM surfaces.

Self-assembled organic and fullerene monolayers characterisation by two-colour SFG spectroscopy: a pathway to meet doubly resonant SFG process

NASA Astrophysics Data System (ADS)

Humbert, C.; Caudano, Y.; Dreesen, L.; Sartenaer, Y.; Mani, A. A.; Silien, C.; Lemaire, J.-J.; Thiry, P. A.; Peremans, A.

2004-10-01

Two-colour sum-frequency generation (two-colour SFG) spectroscopy was used to probe both vibrational and electronic properties of 1-dodecanethiol/Ag(1 1 1), Au(1 1 1), and Pt(1 1 1), of 5-[ p-(6-mercaptohexoxy)-phenyl]-10,15,20-triphenylporphin/Pt(1 1 1), and of C 60/Ag(1 1 1). The role of the various physical parameters determining the sum-frequency generation (SFG) intensity equation is highlighted. The enhancement of the non-linear second order susceptibility in the aforementioned interfaces is explained in terms of metal interband transition, molecular electronic transition and of electron-phonon coupling, respectively.

Mid-infrared multi-mode absorption spectroscopy, MUMAS, using difference frequency generation

NASA Astrophysics Data System (ADS)

Northern, Henry; O'Hagan, Seamus; Hamilton, Michelle L.; Ewart, Paul

2015-03-01

Multi-mode absorption spectroscopy of ammonia and methane at 3.3 μm has been demonstrated using a source of multi-mode mid-infrared radiation based on difference frequency generation. Multi-mode radiation at 1.56 μm from a diode-pumped Er:Yb:glass laser was mixed with a single-mode Nd:YAG laser at 1.06 μm in a periodically poled lithium niobate crystal to produce multi-mode radiation in the region of 3.3 μm. Detection, by direct multi-mode absorption, of NH3 and CH4 is reported for each species individually and also simultaneously in mixtures allowing measurements of partial pressures of each species.

Adding a dimension to the infrared spectra of interfaces: 2D SFG spectroscopy via mid-IR pulse shaping

NASA Astrophysics Data System (ADS)

Zanni, Martin

2012-02-01

Sum-frequency generation spectroscopy provides an infrared spectrum of interfaces and thus has widespread use in the materials and chemical sciences. In this presentation, I will present our recent work in developing a 2D pulse sequence to generate 2D SFG spectra of interfaces, in analogy to 2D infrared spectra used to measure bulk species. To develop this spectroscopy, we have utilized many of the tricks-of-the-trade developed in the 2D IR and 2D Vis communities in the last decade, including mid-IR pulse shaping. With mid-IR pulse shaping, the 2D pulse sequence is manipulated by computer programming in the desired frequency resolution, rotating frame, and signal pathway. We believe that 2D SFG will become an important tool in the interfacial sciences in an analogous way that 2D IR is now being used in many disciplines.

In situ sum-frequency generation spectroscopy of ethylene-glycol and poly-N-isopropylacrylamide films

NASA Astrophysics Data System (ADS)

Kurz, Volker; Koelsch, Patrick

2009-03-01

Ethylene-glycol(EG)-based self-assembled monolayers (SAMs) are often used as a model systems for thin liquid films. Temperature series in heavy water were measured using a unique sample cell developed for in situ sum-frequency generation (SFG) spectroscopy experiments. Results obtained from model EG-SAMs with different lengths and terminating groups in various ionic solutions showed temperature-dependent changes in the molecular order. Films of poly-N-isopropylacrylamide(pNIPAM) were also characterized by in situ SFG spectroscopy in the CH, OH, OD and amide spectral regions under different polarization combinations. These systems have many applications as thermo-responsive polymers due to their ability to change solubility in water at the biologically relevant temperature of 32 C. This so-called lower critical solution temperature (LCST) phase transition was characterized in depth, allowing for the identification of the molecular groups involved in this process.

Coherent radio-frequency detection for narrowband direct comb spectroscopy.

PubMed

Anstie, James D; Perrella, Christopher; Light, Philip S; Luiten, Andre N

2016-02-22

We demonstrate a scheme for coherent narrowband direct optical frequency comb spectroscopy. An extended cavity diode laser is injection locked to a single mode of an optical frequency comb, frequency shifted, and used as a local oscillator to optically down-mix the interrogating comb on a fast photodetector. The high spectral coherence of the injection lock generates a microwave frequency comb at the output of the photodiode with very narrow features, enabling spectral information to be further down-mixed to RF frequencies, allowing optical transmittance and phase to be obtained using electronics commonly found in the lab. We demonstrate two methods for achieving this step: a serial mode-by-mode approach and a parallel dual-comb approach, with the Cs D1 transition at 894 nm as a test case.

Frequency modulation spectroscopy with a THz quantum-cascade laser.

PubMed

Eichholz, R; Richter, H; Wienold, M; Schrottke, L; Hey, R; Grahn, H T; Hübers, H-W

2013-12-30

We report on a terahertz spectrometer for high-resolution molecular spectroscopy based on a quantum-cascade laser. High-frequency modulation (up to 50 MHz) of the laser driving current produces a simultaneous modulation of the frequency and amplitude of the laser output. The modulation generates sidebands, which are symmetrically positioned with respect to the laser carrier frequency. The molecular transition is probed by scanning the sidebands across it. In this way, the absorption and the dispersion caused by the molecular transition are measured. The signals are modeled by taking into account the simultaneous modulation of the frequency and amplitude of the laser emission. This allows for the determination of the strength of the frequency as well as amplitude modulation of the laser and of molecular parameters such as pressure broadening.

Acoustic resonance phase locked photoacoustic spectrometer

DOEpatents

Pilgrim, Jeffrey S.; Bomse, David S.; Silver, Joel A.

2003-08-19

A photoacoustic spectroscopy method and apparatus for maintaining an acoustic source frequency on a sample cell resonance frequency comprising: providing an acoustic source to the sample cell to generate a photoacoustic signal, the acoustic source having a source frequency; continuously measuring detection phase of the photoacoustic signal with respect to source frequency or a harmonic thereof; and employing the measured detection phase to provide magnitude and direction for correcting the source frequency to the resonance frequency.

Time-domain SFG spectroscopy using mid-IR pulse shaping: practical and intrinsic advantages.

PubMed

Laaser, Jennifer E; Xiong, Wei; Zanni, Martin T

2011-03-24

Sum-frequency generation (SFG) spectroscopy is a ubiquitous tool in the surface sciences. It provides infrared transition frequencies and line shapes that probe the structure and environment of molecules at interfaces. In this article, we apply techniques learned from the multidimensional spectroscopy community to SFG spectroscopy. We implement balanced heterodyne detection to remove scatter and the local oscillator background. Heterodyning also separates the resonant and nonresonant signals by acquiring both the real and imaginary parts of the spectrum. We utilize mid-IR pulse shaping to control the phase and delay of the mid-IR pump pulse. Pulse shaping allows phase cycling for data collection in the rotating frame and additional background subtraction. We also demonstrate time-domain data collection, which is a Fourier transform technique, and has many advantages in signal throughput, frequency resolution, and line shape accuracy over existing frequency domain methods. To demonstrate time-domain SFG spectroscopy, we study an aryl isocyanide on gold, and find that the system has an inhomogeneous structural distribution, in agreement with computational results, but which was not resolved by previous frequency-domain SFG studies. The ability to rapidly and actively manipulate the mid-IR pulse in an SFG pules sequence makes possible new experiments and more accurate spectra. © 2011 American Chemical Society

Metrological-grade tunable coherent source in the mid-infrared for molecular precision spectroscopy

NASA Astrophysics Data System (ADS)

Insero, G.; Clivati, C.; D'Ambrosio, D.; Cancio Pastor, P.; Verde, M.; Schunemann, P. G.; Zondy, J.-J.; Inguscio, M.; Calonico, D.; Levi, F.; De Natale, P.; Santambrogio, G.; Borri, S.

2018-02-01

We report on a metrological-grade mid-IR source with a 10-14 short-term instability for high-precision spectroscopy. Our source is based on the combination of a quantum cascade laser and a coherent radiation obtained by difference-frequency generation in an orientation-patterned gallium phosphide (OP-GaP) crystal. The pump and signal lasers are locked to an optical frequency comb referenced to the primary frequency standard via an optical fiber link. We demonstrate the robustness of the apparatus by measuring a vibrational transition around 6 μm on a metastable state of CO molecuels with 11 digits of precision.

Gas spectroscopy system with 245 GHz transmitter and receiver in SiGe BiCMOS

NASA Astrophysics Data System (ADS)

Schmalz, Klaus; Rothbart, Nick; Borngräber, Johannes; Yilmaz, Selahattin Berk; Kissinger, Dietmar; Hübers, Heinz-Wilhelm

2017-02-01

The implementation of an integrated mm-wave transmitter (TX) and receiver (RX) in SiGe BiCMOS or CMOS technology offers a path towards a compact and low-cost system for gas spectroscopy. Previously, we have demonstrated TXs and RXs for spectroscopy at 238 -252 GHz and 495 - 497 GHz using external phase-locked loops (PLLs) with signal generators for the reference frequency ramps. Here, we present a more compact system by using two external fractional-N PLLs allowing frequency ramps for the TX and RX, and for TX with superimposed frequency shift keying (FSK) or reference frequency modulation realized by a direct digital synthesizer (DDS) or an arbitrary waveform generator. The 1.9 m folded gas absorption cell, the vacuum pumps, as well as the TX and RX are placed on a portable breadboard with dimensions of 75 cm x 45 cm. The system performance is evaluated by high-resolution absorption spectra of gaseous methanol at 13 Pa for 241 - 242 GHz. The 2f (second harmonic) content of the absorption spectrum of the methanol was obtained by detecting the IF power of RX using a diode power sensor connected to a lock-in amplifier. The reference frequency modulation reveals a higher SNR (signal-noise-ratio) of 98 within 32 s acquisition compared to 66 for FSK. The setup allows for jumping to preselected frequency regions according to the spectral signature thus reducing the acquisition time by up to one order of magnitude.

Particle formation in SiOx film deposition by low frequency plasma enhanced chemical vapor deposition

NASA Astrophysics Data System (ADS)

Yamaguchi, Tomoyo; Sakamoto, Naoshi; Shimozuma, Mitsuo; Yoshino, Masaki; Tagashira, Hiroaki

1998-01-01

Dust particle formation dynamics in the process of SiOx film deposition from a SiH4 and N2O gas mixture by a low frequency plasma enhanced chemical vapor deposition have been investigated using scanning electron microscopy and laser light scattering. The deposited films are confirmed to be SiOx from the measurements of Auger electron spectroscopy, x-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. It is observed by scanning electron microscopy that particles are deposited on Si substrate at the plasma power frequency f=5 kHz and above both with and without substrate heating (400 °C), while no particle is deposited below f=1 kHz. Moreover, the laser light scattering indicates that particles are generated at the plasma power frequency of f=3 kHz and above in the gas phase, and that they are not generated in the gas phase at below f=3 kHz. Properties (the refractive index, resistivity, and Vickers hardness) of the films with particles are inferior to those of the films without particles. This article has revealed experimentally the effect of plasma power frequency on SiOx particle formation and makes a contribution to the explication of the particle formation mechanism. We suggest that high-quality film deposition with the low frequency plasma enhanced chemical vapor deposition method is attained at f=1 kHz or less without substrate heating.

THz Acoustic Spectroscopy by using Double Quantum Wells and Ultrafast Optical Spectroscopy.

PubMed

Wei, Fan Jun; Yeh, Yu-Hsiang; Sheu, Jinn-Kong; Lin, Kung-Hsuan

2016-06-27

GaN is a pivotal material for acoustic transducers and acoustic spectroscopy in the THz regime, but its THz phonon properties have not been experimentally and comprehensively studied. In this report, we demonstrate how to use double quantum wells as a THz acoustic transducer for measuring generated acoustic phonons and deriving a broadband acoustic spectrum with continuous frequencies. We experimentally investigated the sub-THz frequency dependence of acoustic attenuation (i.e., phonon mean-free paths) in GaN, in addition to its physical origins such as anharmonic scattering, defect scattering, and boundary scattering. A new upper limit of attenuation caused by anharmonic scattering, which is lower than previously reported values, was obtained. Our results should be noteworthy for THz acoustic spectroscopy and for gaining a fundamental understanding of heat conduction.

Interpreting Quasi-Thermal Effects in Ultrafast Spectroscopy of Hydrogen-Bonded Systems.

PubMed

Stingel, Ashley M; Petersen, Poul B

2018-03-15

Vibrational excitation of molecules in the condensed phase relaxes through vibrational modes of decreasing energy to ultimately generate an equilibrium state in which the energy is distributed among low-frequency modes. In ultrafast vibrational spectroscopy, changes in the vibrational features of hydrogen-bonded NH and OH stretch modes are typically observed to persist long after these high-frequency vibrations have relaxed. Due to the resemblance to the spectral changes caused by heating the sample, these features are typically described as arising from a hot ground state. However, these spectral features appear on ultrafast time scales that are much too fast to result from a true thermal state, and significant differences between the thermal difference spectrum and the induced quasi-thermal changes in ultrafast spectroscopy are often observed. Here, we examine and directly compare the thermal and quasi-thermal responses of the hydrogen-bonded homodimer of 7-azaindole with temperature-dependent FTIR spectroscopy and ultrafast mid-IR continuum spectroscopy. We find that the thermal difference spectra contain contributions from both dissociation of the hydrogen bonds and from frequency shifts due to changes in the thermal population of low-frequency modes. The transient spectra in ultrafast vibrational spectroscopy are also found to contain two contributions: initial frequency shifts over 2.3 ± 0.11 ps associated with equilibration of the initial excitation, and frequency shifts associated with the excitation of several fingerprint modes, which decay over 21.8 ± 0.11 ps, giving rise to a quasi-thermal response caused by a distribution of fingerprint modes being excited within the sample ensemble. This resembles the thermal frequency shifts due to population changes of low-frequency modes, but not the overall thermal spectrum, which is dominated by features caused by dimer dissociation. These findings provide insight into the changes in the vibrational spectrum from different origins and are important for assigning, analyzing, and comparing features in thermal and ultrafast vibrational spectroscopy of hydrogen-bonded complexes.

Combined IR-Raman vs vibrational sum-frequency heterospectral correlation spectroscopy

NASA Astrophysics Data System (ADS)

Roy, Sandra; Beutier, Clémentine; Hore, Dennis K.

2018-06-01

Vibrational sum-frequency generation spectroscopy is a valuable probe of surface structure, particularly when the same molecules are present in one of the adjacent bulk solid or solution phases. As a result of the non-centrosymmetric requirement of SFG, the signal generated is a marker of the extent to which the molecules are ordered in an arrangement that breaks the up-down symmetry at the surface. In cases where the accompanying changes in the bulk are of interest in understanding and interpreting the surface structure, simultaneous analysis of the bulk IR absorption or bulk Raman scattering is helpful, and may be used in heterospectral surface-bulk two-dimensional correlation. We demonstrate that, in such cases, generating a new type of bulk spectrum that combines the IR and Raman amplitudes is a better candidate than the individual IR and Raman spectra for the purpose of correlation with the SFG signal.

Enhancement cavities for zero-offset-frequency pulse trains.

PubMed

Holzberger, S; Lilienfein, N; Trubetskov, M; Carstens, H; Lücking, F; Pervak, V; Krausz, F; Pupeza, I

2015-05-15

The optimal enhancement of broadband optical pulses in a passive resonator requires a seeding pulse train with a specific carrier-envelope-offset frequency. Here, we control the phase of the cavity mirrors to tune the offset frequency for which a given comb is optimally enhanced. This enables the enhancement of a zero-offset-frequency train of sub-30-fs pulses to multi-kW average powers. The combination of pulse duration, power, and zero phase slip constitutes a crucial step toward the generation of attosecond pulses at multi-10-MHz repetition rates. In addition, this control affords the enhancement of pulses generated by difference-frequency mixing, e.g., for mid-infrared spectroscopy.

Vibrational sum frequency generation (SFG) spectroscopic study of crystalline cellulose in biomass

NASA Astrophysics Data System (ADS)

Kim, Seong H.; Lee, Christopher M.; Kafle, Kabindra; Park, Yong Bum; Xi, Xiaoning

2013-09-01

The noncentrosymmetry requirement of sum frequency generation (SFG) spectroscopy allows selective detection of crystalline cellulose in plant cell walls and lignocellulose biomass without spectral interferences from hemicelluloses and lignin. In addition, the phase synchronization requirement of the SFG process allows noninvasive investigation of spatial arrangement of crystalline cellulose microfibrils in the sample. This paper reviews how these principles are applied to reveal structural information of crystalline cellulose in plant cell walls and biomass.

Fully stabilized mid-infrared frequency comb for high-precision molecular spectroscopy.

PubMed

Vainio, Markku; Karhu, Juho

2017-02-20

A fully stabilized mid-infrared optical frequency comb spanning from 2.9 to 3.4 µm is described in this article. The comb is based on half-harmonic generation in a femtosecond optical parametric oscillator, which transfers the high phase coherence of a fully stabilized near-infrared Er-doped fiber laser comb to the mid-infrared region. The method is simple, as no phase-locked loops or reference lasers are needed. Precise locking of optical frequencies of the mid-infrared comb to the pump comb is experimentally verified at sub-20 mHz level, which corresponds to a fractional statistical uncertainty of 2 × 10^-16 at the center frequency of the mid-infrared comb. The fully stabilized mid-infrared comb is an ideal tool for high-precision molecular spectroscopy, as well as for optical frequency metrology in the mid-infrared region, which is difficult to access with other stabilized frequency comb techniques.

Wide-Range Filter-Based Sinusoidal Wave Synthesizer for Electrochemical Impedance Spectroscopy Measurements.

PubMed

Chia-Ling Wei; Yi-Wen Wang; Bin-Da Liu

2014-06-01

A filter-based wide-range programmable sinusoidal wave synthesizer for electrochemical impedance spectroscopy measurement is proposed. The adopted filter is implemented with switched-capacitor circuits, so its corner frequency is accurate and adjustable by changing its switching frequency. The proposed sine wave synthesizer is implemented by using a 0.35 μm 2P4M 3.3 V mixed-signal polycide process. According to the measured results, the output frequency of the proposed synthesizer is 40 mHz-40 kHz . The measured total harmonic distortion is 0.073% at 10 Hz and 0.075% at 10 kHz, both of which are better than that of a typical function generator.

Electrochemical impedance spectroscopy of supercapacitors: A novel analysis approach using evolutionary programming

NASA Astrophysics Data System (ADS)

Oz, Alon; Hershkovitz, Shany; Tsur, Yoed

2014-11-01

In this contribution we present a novel approach to analyze impedance spectroscopy measurements of supercapacitors. Transforming the impedance data into frequency-dependent capacitance allows us to use Impedance Spectroscopy Genetic Programming (ISGP) in order to find the distribution function of relaxation times (DFRT) of the processes taking place in the tested device. Synthetic data was generated in order to demonstrate this technique and a model for supercapacitor ageing process has been obtained.

Optical Frequency Synthesizer for Precision Spectroscopy

NASA Astrophysics Data System (ADS)

Holzwarth, R.; Udem, Th.; Hänsch, T. W.; Knight, J. C.; Wadsworth, W. J.; Russell, P. St. J.

2000-09-01

We have used the frequency comb generated by a femtosecond mode-locked laser and broadened to more than an optical octave in a photonic crystal fiber to realize a frequency chain that links a 10 MHz radio frequency reference phase-coherently in one step to the optical region. By comparison with a similar frequency chain we set an upper limit for the uncertainty of this new approach to 5.1×10-16. This opens the door for measurement and synthesis of virtually any optical frequency and is ready to revolutionize frequency metrology.

Direct Spectroscopy in Hollow Optical with Fiber-Based Optical Frequency Combs

DTIC Science & Technology

2015-07-09

scheme is that the generation of carrier-envelope offset frequency f0 can be avoided, which reduces the system complexity . However, a high performance RF...Peterson, "Saturated absorption in acetylene and hydrogen cyanide in hollow-core photonic bandgap fibers," Opt. Express 13, 10475-10482 (2005). 56. C

Quantum cascade lasers: from tool to product.

PubMed

Razeghi, M; Lu, Q Y; Bandyopadhyay, N; Zhou, W; Heydari, D; Bai, Y; Slivken, S

2015-04-06

The quantum cascade laser (QCL) is an important laser source in the mid-infrared and terahertz frequency range. The past twenty years have witnessed its tremendous development in power, wall plug efficiency, frequency coverage and tunability, beam quality, as well as various applications based on QCL technology. Nowadays, QCLs can deliver high continuous wave power output up to 5.1 W at room temperature, and cover a wide frequency range from 3 to 300 μm by simply varying the material components. Broadband heterogeneous QCLs with a broad spectral range from 3 to 12 μm, wavelength agile QCLs based on monolithic sampled grating design, and on-chip beam QCL combiner are being developed for the next generation tunable mid-infrared source for spectroscopy and sensing. Terahertz sources based on nonlinear generation in QCLs further extend the accessible wavelength into the terahertz range. Room temperature continuous wave operation, high terahertz power up to 1.9 mW, and wide frequency tunability form 1 to 5 THz makes this type of device suitable for many applications in terahertz spectroscopy, imaging, and communication.

Multiharmonic Frequency-Chirped Transducers for Surface-Acoustic-Wave Optomechanics

NASA Astrophysics Data System (ADS)

Weiß, Matthias; Hörner, Andreas L.; Zallo, Eugenio; Atkinson, Paola; Rastelli, Armando; Schmidt, Oliver G.; Wixforth, Achim; Krenner, Hubert J.

2018-01-01

Wide-passband interdigital transducers are employed to establish a stable phase lock between a train of laser pulses emitted by a mode-locked laser and a surface acoustic wave generated electrically by the transducer. The transducer design is based on a multiharmonic split-finger architecture for the excitation of a fundamental surface acoustic wave and a discrete number of its overtones. Simply by introducing a variation of the transducer's periodicity p , a frequency chirp is added. This combination results in wide frequency bands for each harmonic. The transducer's conversion efficiency from the electrical to the acoustic domain is characterized optomechanically using single quantum dots acting as nanoscale pressure sensors. The ability to generate surface acoustic waves over a wide band of frequencies enables advanced acousto-optic spectroscopy using mode-locked lasers with fixed repetition rate. Stable phase locking between the electrically generated acoustic wave and the train of laser pulses is confirmed by performing stroboscopic spectroscopy on a single quantum dot at a frequency of 320 MHz. Finally, the dynamic spectral modulation of the quantum dot is directly monitored in the time domain combining stable phase-locked optical excitation and time-correlated single-photon counting. The demonstrated scheme will be particularly useful for the experimental implementation of surface-acoustic-wave-driven quantum gates of optically addressable qubits or collective quantum states or for multicomponent Fourier synthesis of tailored nanomechanical waveforms.

Doubly resonant three-wave-mixing spectroscopy of a chiral coupled-chromophore system in solution: coherent two-dimensional optical activity spectroscopy.

PubMed

Cheon, Sangheon; Lee, Hochan; Choi, Jun-Ho; Cho, Minhaeng

2007-02-07

Theoretical descriptions of doubly resonant two-dimensional (2D) sum-frequency-generation (SFG) and difference-frequency-generation (DFG) spectroscopies of coupled-chromophore systems are presented. Despite that each electronic or vibrational chromophore is achiral, the interaction-induced chirality of a coupled multichromophore system in solution can be measured by using the doubly resonant 2D three-wave-mixing (3WM) spectroscopic method. An electronically coupled dimer, where each monomer is modeled as a simple two-level system, can have nonvanishing SFG (or DFG) properties, e.g., susceptibility in frequency domain or nonlinear response function in time domain, if the induced dipole vector of the dimer is not orthogonal to the vector product of the two monomer electronic transition dipole vectors. In order to demonstrate that these 2D 3WM spectroscopic methods can be used to determine the solution structure of a polypeptide, the authors carried out quantum chemistry calculations for an alanine dipeptide and obtained first- and second-order dipole derivatives associated with the amide I vibrational transitions of the dipeptide. It is shown that the numerically simulated 2D IR-IR SFG spectrum is highly sensitive to the dipeptide secondary structure and provides rich information on the one- and two-exciton states. It is believed that the theoretically proposed doubly resonant 2D 3WM spectroscopy, which can be considered to be an optical activity spectroscopy, will be of use in studying both structural and dynamical aspects of coupled multichromophore systems, such as proteins, nucleic acids, nanoparticle aggregates etc.

High-Resolution Dual-Comb Spectroscopy with Ultra-Low Noise Frequency Combs

NASA Astrophysics Data System (ADS)

Hänsel, Wolfgang; Giunta, Michele; Beha, Katja; Perry, Adam J.; Holzwarth, R.

2017-06-01

Dual-comb spectroscopy is a powerful tool for fast broad-band spectroscopy due to the parallel interrogation of thousands of spectral lines. Here we report on the spectroscopic analysis of acetylene vapor in a pressurized gas cell using two ultra-low noise frequency combs with a repetition rate around 250 MHz. Optical referencing to a high-finesse cavity yields a sub-Hertz stability of all individual comb lines (including the virtual comb lines between 0 Hz and the carrier) and permits one to pick a small difference of repetition rate for the two frequency combs on the order of 300 Hz, thus representing an optical spectrum of 100 THz (˜3300 \\wn) within half the free spectral range (125 MHz). The transmission signal is derived straight from a photodetector and recorded with a high-resolution spectrum analyzer or digitized with a computer-controlled AD converter. The figure to the right shows a schematic of the experimental setup which is all fiber-coupled with polarization-maintaining fiber except for the spectroscopic cell. The graph on the lower right reveals a portion of the recorded radio-frequency spectrum which has been scaled to the optical domain. The location of the measured absorption coincides well with data taken from the HITRAN data base. Due to the intrinsic linewidth of all contributing comb lines, each sampling point in the transmission graph corresponds to the probing at an optical frequency with sub-Hertz resolution. This resolution is maintained in coherent wavelength conversion processes such as difference-frequency generation (DFG), sum-frequency generation (SFG) or non-linear broadening (self-phase modulation), and is therefore easily transferred to a wide spectral range from the mid infrared up to the visible spectrum.

Oxidation-Resistant Surfaces For Solar Reflectors

NASA Technical Reports Server (NTRS)

Gulino, Daniel A.; Egger, Robert A.; Banholzer, William F.

1988-01-01

Thin films on silver provide highly-reflective, corrosion-resistant mirrors. Study evaluated variety of oxidation-resistant reflective materials for use in solar dynamic power system, one that generates electricity by focusing Sunlight onto reciever of heat engine. Thin films of platinum and rhodium deposited by ion-beam sputtering on various substrate materials. Solar reflectances measured as function of time of exposure to radio-frequency-generated air plasma. Several protective coating materials deposited on silver-coated substrates and exposed to plasma. Analyzed before and after exposure by electon spectroscopy for chemical analysis and by Auger spectroscopy.

Communication: atomic force detection of single-molecule nonlinear optical vibrational spectroscopy.

PubMed

Saurabh, Prasoon; Mukamel, Shaul

2014-04-28

Atomic Force Microscopy (AFM) allows for a highly sensitive detection of spectroscopic signals. This has been first demonstrated for NMR of a single molecule and recently extended to stimulated Raman in the optical regime. We theoretically investigate the use of optical forces to detect time and frequency domain nonlinear optical signals. We show that, with proper phase matching, the AFM-detected signals closely resemble coherent heterodyne-detected signals. Applications are made to AFM-detected and heterodyne-detected vibrational resonances in Coherent Anti-Stokes Raman Spectroscopy (χ((3))) and sum or difference frequency generation (χ((2))).

Resonance ionization spectroscopy of sodium Rydberg levels using difference frequency generation of high-repetition-rate pulsed Ti:sapphire lasers

NASA Astrophysics Data System (ADS)

Naubereit, P.; Marín-Sáez, J.; Schneider, F.; Hakimi, A.; Franzmann, M.; Kron, T.; Richter, S.; Wendt, K.

2016-05-01

The generation of tunable laser light in the green to orange spectral range has generally been a deficiency of solid-state lasers. Hence, the formalisms of difference frequency generation (DFG) and optical parametric processes are well known, but the DFG of pulsed solid-state lasers was rarely efficient enough for its use in resonance ionization spectroscopy. Difference frequency generation of high-repetition-rate Ti:sapphire lasers was demonstrated for resonance ionization of sodium by efficiently exciting the well-known D1 and D2 lines in the orange spectral range (both ≈589 nm). In order to prove the applicability of the laser system for its use at resonance ionization laser ion sources of radioactive ion beam facilities, the first ionization potential of Na was remeasured by three-step resonance ionization into Rydberg levels and investigating Rydberg convergences. A result of EIP=41449.455 (6) stat(7) syscm-1 was obtained, which is in perfect agreement with the literature value of EIPlit =41449.451(2)cm-1 . A total of 41 level positions for the odd-parity Rydberg series n f 2F5/2,7/2o for principal quantum numbers of 10 ≤n ≤60 were determined experimentally.

Real-time dual-comb spectroscopy with a free-running bidirectionally mode-locked fiber laser

NASA Astrophysics Data System (ADS)

Mehravar, S.; Norwood, R. A.; Peyghambarian, N.; Kieu, K.

2016-06-01

Dual-comb technique has enabled exciting applications in high resolution spectroscopy, precision distance measurements, and 3D imaging. Major advantages over traditional methods can be achieved with dual-comb technique. For example, dual-comb spectroscopy provides orders of magnitude improvement in acquisition speed over standard Fourier-transform spectroscopy while still preserving the high resolution capability. Wider adoption of the technique has, however, been hindered by the need for complex and expensive ultrafast laser systems. Here, we present a simple and robust dual-comb system that employs a free-running bidirectionally mode-locked fiber laser operating at telecommunication wavelength. Two femtosecond frequency combs (with a small difference in repetition rates) are generated from a single laser cavity to ensure mutual coherent properties and common noise cancellation. As the result, we have achieved real-time absorption spectroscopy measurements without the need for complex servo locking with accurate frequency referencing, and relatively high signal-to-noise ratio.

Selective detection of crystalline cellulose in plant cell walls with sum-frequency-generation (SFG) vibration spectroscopy.

PubMed

Barnette, Anna L; Bradley, Laura C; Veres, Brandon D; Schreiner, Edward P; Park, Yong Bum; Park, Junyeong; Park, Sunkyu; Kim, Seong H

2011-07-11

The selective detection of crystalline cellulose in biomass was demonstrated with sum-frequency-generation (SFG) vibration spectroscopy. SFG is a second-order nonlinear optical response from a system where the optical centrosymmetry is broken. In secondary plant cell walls that contain mostly cellulose, hemicellulose, and lignin with varying concentrations, only certain vibration modes in the crystalline cellulose structure can meet the noninversion symmetry requirements. Thus, SFG can be used to detect and analyze crystalline cellulose selectively in lignocellulosic biomass without extraction of noncellulosic species from biomass or deconvolution of amorphous spectra. The selective detection of crystalline cellulose in lignocellulosic biomass is not readily achievable with other techniques such as XRD, solid-state NMR, IR, and Raman analyses. Therefore, the SFG analysis presents a unique opportunity to reveal the cellulose crystalline structure in lignocellulosic biomass.

THz acoustic phonon spectroscopy and nanoscopy by using piezoelectric semiconductor heterostructures.

PubMed

Mante, Pierre-Adrien; Huang, Yu-Ru; Yang, Szu-Chi; Liu, Tzu-Ming; Maznev, Alexei A; Sheu, Jinn-Kong; Sun, Chi-Kuang

2015-02-01

Thanks to ultrafast acoustics, a better understanding of acoustic dynamics on a short time scale has been obtained and new characterization methods at the nanoscale have been developed. Among the materials that were studied during the development of ultrafast acoustics, nitride based heterostructures play a particular role due to their piezoelectric properties and the possibility to generate phonons with over-THz frequency and bandwidth. Here, we review some of the work performed using this type of structure, with a focus on THz phonon spectroscopy and nanoscopy. First, we present a brief description of the theory of coherent acoustic phonon generation by piezoelectric heterostructure. Then the first experimental observation of coherent acoustic phonon generated by the absorption of ultrashort light pulses in piezoelectric heterostructures is presented. From this starting point, we then present some methods developed to realize customizable phonon generation. Finally we review some more recent applications of these structures, including imaging with a nanometer resolution, broadband attenuation measurements with a frequency up to 1THz and phononic bandgap characterization. Copyright © 2014 Elsevier B.V. All rights reserved.

Inhomogeneity of Cellulose Microfibril Assembly in Plant Cell Walls Revealed with Sum Frequency Generation Microscopy.

PubMed

Huang, Shixin; Makarem, Mohamadamin; Kiemle, Sarah N; Hamedi, Hossein; Sau, Moujhuri; Cosgrove, Daniel J; Kim, Seong H

2018-05-17

Sum frequency generation (SFG) vibrational spectroscopy can selectively detect and analyze noncentrosymmetric components interspersed in amorphous matrices; this principle has been used for studies of nanoscale structure and mesoscale assembly of cellulose in plant cell walls. However, the spectral information averaged over a large area or volume cannot provide regiospecific or tissue-specific information of different cells in plants. This study demonstrates spatially resolved SFG analysis and imaging by combining a broad-band SFG spectroscopy system with an optical microscope. The system was designed to irradiate both narrow-band 800 nm and broad-band tunable IR beams through a single reflective objective lens, but from opposite sides of the surface normal direction of the sample. The developed technique was used to reveal inhomogeneous distributions of cellulose microfibrils within single cell walls, such as cotton fibers and onion epidermis as well as among different tissues in Arabidopsis inflorescence stems and bamboo culms. SFG microscopy can be used for vibrational spectroscopic imaging of other biological systems in complement to conventional Fourier transform infrared spectroscopy and confocal Raman microscopy.

Optical pathology of human brain metastasis of lung cancer using combined resonance Raman and spatial frequency spectroscopies

NASA Astrophysics Data System (ADS)

Zhou, Yan; Liu, Cheng-hui; Pu, Yang; Cheng, Gangge; Zhou, Lixin; Chen, Jun; Zhu, Ke; Alfano, Robert R.

2016-03-01

Raman spectroscopy has become widely used for diagnostic purpose of breast, lung and brain cancers. This report introduced a new approach based on spatial frequency spectra analysis of the underlying tissue structure at different stages of brain tumor. Combined spatial frequency spectroscopy (SFS), Resonance Raman (RR) spectroscopic method is used to discriminate human brain metastasis of lung cancer from normal tissues for the first time. A total number of thirty-one label-free micrographic images of normal and metastatic brain cancer tissues obtained from a confocal micro- Raman spectroscopic system synchronously with examined RR spectra of the corresponding samples were collected from the identical site of tissue. The difference of the randomness of tissue structures between the micrograph images of metastatic brain tumor tissues and normal tissues can be recognized by analyzing spatial frequency. By fitting the distribution of the spatial frequency spectra of human brain tissues as a Gaussian function, the standard deviation, σ, can be obtained, which was used to generate a criterion to differentiate human brain cancerous tissues from the normal ones using Support Vector Machine (SVM) classifier. This SFS-SVM analysis on micrograph images presents good results with sensitivity (85%), specificity (75%) in comparison with gold standard reports of pathology and immunology. The dual-modal advantages of SFS combined with RR spectroscopy method may open a new way in the neuropathology applications.

Phase Acrobatics: The Influence of Excitonic Resonance and Gold Nonresonant Background on Heterodyne-Detected Vibrational Sum Frequency Generation Emission.

PubMed

Rich, Christopher C; Lindberg, Kathryn A; Krummel, Amber T

2017-04-06

We show how heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy can discriminate between the excitonic and monomeric properties of a helical, nanotube molecular aggregate by monitoring the phase of the VSFG emission associated with different polarization configurations. By keeping track of the "phase acrobatics" associated with the added phase of the nonresonant SFG emission of gold as well as that of the double-resonance conditions achieved when the SF frequency is resonant with an electronic exciton transition, we discover that for aggregates of tetra(sulfonatophenyl)porphyrin (TSPP) the PPP-polarized spectra exhibit double-resonance conditions while SSP-polarized spectra exhibit resonance only with the ground-state vibration. Along with observed shifts in the vibrational frequency, intensity differences, and sign flips in the imaginary second-order susceptibility, χ s,Im (2) , we conclude that PPP-polarized HD-VSFG spectra reflect the delocalized, excitonic nature of the molecular aggregate, while the SSP-polarized HD-VSFG spectra measure the localized, monomeric nature of the molecular subunits. It is implied from this study that HD-VSFG spectroscopy can be uniquely utilized to measure the excitonic and monomeric properties associated with molecular assemblies for a single sample.

Ultra-broadband THz time-domain spectroscopy of common polymers using THz air photonics.

PubMed

D'Angelo, Francesco; Mics, Zoltán; Bonn, Mischa; Turchinovich, Dmitry

2014-05-19

Terahertz-range dielectric properties of the common polymers low-density polyethylene (LDPE), cyclic olefin/ethylene copolymer (TOPAS®), polyamide-6 (PA6), and polytetrafluoroethylene (PTFE or Teflon®) are characterized in the ultra-broadband frequency window 2-15 THz, using a THz time-domain spectrometer employing air-photonics for the generation and detection of single-cycle sub-50 fs THz transients. The time domain measurements provide direct access to both the absorption and refractive index spectra. The polymers LDPE and TOPAS® demonstrate negligible absorption and spectrally-flat refractive index across the entire spectroscopy window, revealing the high potential of these polymers for applications in THz photonics such as ultra-broadband polymer-based dielectric mirrors, waveguides, and fibers. Resonant high-frequency polar vibrational modes are observed and assigned in polymers PA6 and PTFE, and their dielectric functions in the complete frequency window 2-15 THz are theoretically reproduced. Our results demonstrate the potential of ultra-broadband air-photonics-based THz time domain spectroscopy as a valuable analytic tool for materials science.

Copper ESEEM and HYSCORE through ultra-wideband chirp EPR spectroscopy.

PubMed

Segawa, Takuya F; Doll, Andrin; Pribitzer, Stephan; Jeschke, Gunnar

2015-07-28

The main limitation of pulse electron paramagnetic resonance (EPR) spectroscopy is its narrow excitation bandwidth. Ultra-wideband (UWB) excitation with frequency-swept chirp pulses over several hundreds of megahertz overcomes this drawback. This allows to excite electron spin echo envelope modulation (ESEEM) from paramagnetic copper centers in crystals, whereas up to now, only ESEEM of ligand nuclei like protons or nitrogens at lower frequencies could be detected. ESEEM spectra are recorded as two-dimensional correlation experiments, since the full digitization of the electron spin echo provides an additional Fourier transform EPR dimension. Thus, UWB hyperfine-sublevel correlation experiments generate a novel three-dimensional EPR-correlated nuclear modulation spectrum.

A CMOS Self-Contained Quadrature Signal Generator for SoC Impedance Spectroscopy.

PubMed

Márquez, Alejandro; Pérez-Bailón, Jorge; Calvo, Belén; Medrano, Nicolás; Martínez, Pedro A

2018-04-30

This paper presents a low-power fully integrated quadrature signal generator for system-on-chip (SoC) impedance spectroscopy applications. It has been designed in a 0.18 μm-1.8 V CMOS technology as a self-contained oscillator, without the need for an external reference clock. The frequency can be digitally tuned from 10 to 345 kHz with 12-bit accuracy and a relative mean error below 1.7%, thus supporting a wide range of impedance sensing applications. The proposal is experimentally validated in two impedance spectrometry examples, achieving good magnitude and phase recovery results compared to the results obtained using a commercial LCR-meter. Besides the wide frequency tuning range, the proposed programmable oscillator features a total power consumption lower than 0.77 mW and an active area of 0.129 mm², thus constituting a highly suitable choice as stimulation module for instrument-on-a-chip devices.

Resistive spectroscopy coupled with non-contacting oscillator for detecting discontinuous-continuous transition of metallic films

NASA Astrophysics Data System (ADS)

Nakamura, N.; Ogi, H.

2017-09-01

In spectroscopic measurements, one measures responses of specimens to oscillating fields (including electric, magnetic, and stress fields) at different frequencies for characterizing the samples. In contrast, we develop spectroscopy where the response (loss) is measured by changing the electric resistance, named the resistive spectroscopy. In the resistive spectroscopy, an energy-loss peak appears when the resistance is changed. We here apply it for studying the morphological change of thin films. When a metallic material is deposited on a substrate, the morphological transition from discontinuous islands to the continuous film occurs. It accompanies a drastic change in the resistance of the deposited material because of the transition from an insulator to a conductor. We find that the energy-loss peak appears at the transition moment during deposition of Ag. The resistive spectroscopy we develop uses no electrodes; it adopts the electric field generated by a piezoelectric material vibrating at its resonant frequency beneath the substrate. It is observed that the full width at half maximum (FWHM) of the resonance shows the peak during the deposition for high resistance substrates. The FWHM peak fails to be found for low resistance substrates, but it appears when the resonance frequency is increased. We propose an electrical-circuit model for explaining these observations.

Dispersion compensated mid-infrared quantum cascade laser frequency comb with high power output

NASA Astrophysics Data System (ADS)

Lu, Q. Y.; Manna, S.; Slivken, S.; Wu, D. H.; Razeghi, M.

2017-04-01

Chromatic dispersion control plays an underlying role in optoelectronics and spectroscopy owing to its enhancement to nonlinear interactions by reducing the phase mismatching. This is particularly important to optical frequency combs based on quantum cascade lasers which require negligible dispersions for efficient mode locking of the dispersed modes into equally spaced comb modes. Here, we demonstrated a dispersion compensated mid-IR quantum cascade laser frequency comb with high power output at room temperature. A low-loss dispersive mirror has been engineered to compensate the device's dispersion residue for frequency comb generation. Narrow intermode beating linewidths of 40 Hz in the comb-working currents were identified with a high power output of 460 mW and a broad spectral coverage of 80 cm-1. This dispersion compensation technique will enable fast spectroscopy and high-resolution metrology based on QCL combs with controlled dispersion and suppressed noise.

Atmospheric pressure reaction cell for operando sum frequency generation spectroscopy of ultrahigh vacuum grown model catalysts

NASA Astrophysics Data System (ADS)

Roiaz, Matteo; Pramhaas, Verena; Li, Xia; Rameshan, Christoph; Rupprechter, Günther

2018-04-01

A new custom-designed ultrahigh vacuum (UHV) chamber coupled to a UHV and atmospheric-pressure-compatible spectroscopic and catalytic reaction cell is described, which allows us to perform IR-vis sum frequency generation (SFG) vibrational spectroscopy during catalytic (kinetic) measurements. SFG spectroscopy is an exceptional tool to study vibrational properties of surface adsorbates under operando conditions, close to those of technical catalysis. This versatile setup allows performing surface science, SFG spectroscopy, catalysis, and electrochemical investigations on model systems, including single crystals, thin films, and deposited metal nanoparticles, under well-controlled conditions of gas composition, pressure, temperature, and potential. The UHV chamber enables us to prepare the model catalysts and to analyze their surface structure and composition by low energy electron diffraction and Auger electron spectroscopy, respectively. Thereafter, a sample transfer mechanism moves samples under UHV to the spectroscopic cell, avoiding air exposure. In the catalytic cell, SFG spectroscopy and catalytic tests (reactant/product analysis by mass spectrometry or gas chromatography) are performed simultaneously. A dedicated sample manipulation stage allows the model catalysts to be examined from LN2 temperature to 1273 K, with gaseous reactants in a pressure range from UHV to atmospheric. For post-reaction analysis, the SFG cell is rapidly evacuated and samples are transferred back to the UHV chamber. The capabilities of this new setup are demonstrated by benchmark results of CO adsorption on Pt and Pd(111) single crystal surfaces and of CO adsorption and oxidation on a ZrO2 supported Pt nanoparticle model catalyst grown by atomic layer deposition.

Frequency comb SFG: a new approach to multiplex detection.

PubMed

Kearns, Patrick M; Sohrabpour, Zahra; Massari, Aaron M

2016-08-22

Determination of molecular orientation at interfaces by vibrational sum frequency generation spectroscopy (VSFG) requires measurements using at least two different polarization combinations of the incoming visible, IR, and generated SFG beams. We present a new method for the simultaneous collection of different VSFG polarization outputs by use of a modified 4f pulseshaper to create a simple frequency comb. Via the frequency comb, two visible pulses are separated spectrally but aligned in space and time to interact at the sample with mixed polarization IR light. This produces two different VSFG outputs that are separated by their frequencies at the monochromator rather than their polarizations. Spectra were collected from organic thin films with different polarization combinations to show the reliability of the method. The results show that the optical arrangement is immune to fluctuations in laser power, beam pointing, and IR spectral shape.

Frequency-agile dual-comb spectroscopy

NASA Astrophysics Data System (ADS)

Millot, Guy; Pitois, Stéphane; Yan, Ming; Hovhannisyan, Tatevik; Bendahmane, Abdelkrim; Hänsch, Theodor W.; Picqué, Nathalie

2016-01-01

Spectroscopic gas sensing and its applications to, for example, trace detection or chemical kinetics, require ever more demanding measurement times, acquisition rates, sensitivities, precisions and broad tuning ranges. Here, we propose a new approach to near-infrared molecular spectroscopy, utilizing advanced concepts of optical telecommunications and supercontinuum photonics. We generate, without mode-locked lasers, two frequency combs of slightly different repetition frequencies and moderate, but rapidly tunable, spectral span. The output of a frequency-agile continuous-wave laser is split and sent into two electro-optic intensity modulators. Flat-top low-noise frequency combs are produced by wave-breaking in a nonlinear optical fibre of normal dispersion. With a dual-comb spectrometer, we record Doppler-limited spectra spanning 60 GHz within 13 μs and an 80 kHz refresh rate, at a tuning speed of 10 nm s-1. The sensitivity for weak absorption is enhanced by a long gas-filled hollow-core fibre. New opportunities for real-time diagnostics may be opened up, even outside the laboratory.

Beat frequency quartz-enhanced photoacoustic spectroscopy for fast and calibration-free continuous trace-gas monitoring

PubMed Central

Wu, Hongpeng; Dong, Lei; Zheng, Huadan; Yu, Yajun; Ma, Weiguang; Zhang, Lei; Yin, Wangbao; Xiao, Liantuan; Jia, Suotang; Tittel, Frank K.

2017-01-01

Quartz-enhanced photoacoustic spectroscopy (QEPAS) is a sensitive gas detection technique which requires frequent calibration and has a long response time. Here we report beat frequency (BF) QEPAS that can be used for ultra-sensitive calibration-free trace-gas detection and fast spectral scan applications. The resonance frequency and Q-factor of the quartz tuning fork (QTF) as well as the trace-gas concentration can be obtained simultaneously by detecting the beat frequency signal generated when the transient response signal of the QTF is demodulated at its non-resonance frequency. Hence, BF-QEPAS avoids a calibration process and permits continuous monitoring of a targeted trace gas. Three semiconductor lasers were selected as the excitation source to verify the performance of the BF-QEPAS technique. The BF-QEPAS method is capable of measuring lower trace-gas concentration levels with shorter averaging times as compared to conventional PAS and QEPAS techniques and determines the electrical QTF parameters precisely. PMID:28561065

SFG spectroscopy from 10 -8 to 1000 mbar: less-ordered CO structures and coadsorption on Pd (1 1 1)

NASA Astrophysics Data System (ADS)

Morkel, Matthias; Unterhalt, Holger; Salmeron, Miquel; Rupprechter, Günther; Freund, Hans-Joachim

2003-06-01

Vibrational sum frequency generation spectroscopy was employed to study "less-ordered" phases resulting from low-temperature CO exposure on Pd(1 1 1). Such imperfect structures may also occur under catalytic reaction conditions up to 1000 mbar and originate from the superposition of ordered structures when the CO mobility and flux were insufficient. The effect of coadsorbed hydrogen and water was also examined.

Terahertz Frequency-Domain Spectroscopy of Low-Pressure Acetonitrile Gas by a Photomixing Terahertz Synthesizer Referenced to Dual Optical Frequency Combs

NASA Astrophysics Data System (ADS)

Hsieh, Yi-Da; Kimura, Hiroto; Hayashi, Kenta; Minamikawa, Takeo; Mizutani, Yasuhiro; Yamamoto, Hirotsugu; Iwata, Tetsuo; Inaba, Hajime; Minoshima, Kaoru; Hindle, Francis; Yasui, Takeshi

2016-09-01

A terahertz (THz) frequency synthesizer based on photomixing of two near-infrared lasers with a sub-THz to THz frequency offset is a powerful tool for spectroscopy of polar gas molecules due to its broad spectral coverage; however, its frequency accuracy and resolution are relatively low. To tune the output frequency continuously and widely while maintaining its traceability to a frequency standard, we developed a photomixing THz synthesizer phase-locked to dual optical frequency combs (OFCs). While the phase-locking to dual OFCs ensured continuous tuning within a spectral range of 120 GHz, in addition to the traceability to the frequency standard, use of a broadband uni-traveling carrier photodiode for photomixing enabled the generation of CW-THz radiation within a frequency range from 0.2 to 1.5 THz. We demonstrated THz frequency-domain spectroscopy of gas-phase acetonitrile CH3CN and its isotope CH3 13CN in the frequency range of 0.600-0.720 THz using this THz synthesizer. Their rotational transitions were assigned with a frequency accuracy of 8.42 × 10-8 and a frequency resolution of 520 kHz. Furthermore, the concentration of the CH3CN gas at 20 Pa was determined to be (5.41 ± 0.05) × 1014 molecules/cm3 by curve fitting analysis of the measured absorbance spectrum, and the mixture ratio of the mixed CH3CN/CH3 13CN gas was determined to be 1:2.26 with a gas concentration of 1014-1015 molecules/cm3. The developed THz synthesizer is highly promising for high-precision THz-FDS of low-pressure molecular gases and will enable the qualitative and quantitative analyses of multiple gases.

Generalized Autobalanced Ramsey Spectroscopy of Clock Transitions

NASA Astrophysics Data System (ADS)

Yudin, V. I.; Taichenachev, A. V.; Basalaev, M. Yu.; Zanon-Willette, T.; Pollock, J. W.; Shuker, M.; Donley, E. A.; Kitching, J.

2018-05-01

When performing precision measurements, the quantity being measured is often perturbed by the measurement process itself. Such measurements include precision frequency measurements for atomic clock applications carried out with Ramsey spectroscopy. With the aim of eliminating probe-induced perturbations, a method of generalized autobalanced Ramsey spectroscopy (GABRS) is presented and rigorously substantiated. The usual local-oscillator frequency control loop is augmented with a second control loop derived from secondary Ramsey sequences interspersed with the primary sequences and with a different Ramsey period. This second loop feeds back to a secondary clock variable and ultimately compensates for the perturbation of the clock frequency caused by the measurements in the first loop. We show that such a two-loop scheme can lead to perfect compensation for measurement-induced light shifts and does not suffer from the effects of relaxation, time-dependent pulse fluctuations and phase-jump modulation errors that are typical of other hyper-Ramsey schemes. Several variants of GABRS are explored based on different secondary variables including added relative phase shifts between Ramsey pulses, external frequency-step compensation, and variable second-pulse duration. We demonstrate that a universal antisymmetric error signal, and hence perfect compensation at a finite modulation amplitude, is generated only if an additional frequency step applied during both Ramsey pulses is used as the concomitant variable parameter. This universal technique can be applied to the fields of atomic clocks, high-resolution molecular spectroscopy, magnetically induced and two-photon probing schemes, Ramsey-type mass spectrometry, and the field of precision measurements. Some variants of GABRS can also be applied for rf atomic clocks using coherent-population-trapping-based Ramsey spectroscopy of the two-photon dark resonance.

Method And Apparatus For High Resolution Ex-Situ Nmr Spectroscopy

DOEpatents

Pines, Alexander; Meriles, Carlos A.; Heise, Henrike; Sakellariou, Dimitrios; Moule, Adam

2004-01-06

A method and apparatus for ex-situ nuclear magnetic resonance spectroscopy for use on samples outside the physical limits of the magnets in inhomogeneous static and radio-frequency fields. Chemical shift spectra can be resolved with the method using sequences of correlated, composite z-rotation pulses in the presence of spatially matched static and radio frequency field gradients producing nutation echoes. The amplitude of the echoes is modulated by the chemical shift interaction and an inhomogeneity free FID may be recovered by stroboscopically sampling the maxima of the echoes. In an alternative embodiment, full-passage adiabatic pulses are consecutively applied. One embodiment of the apparatus generates a static magnetic field that has a variable saddle point.

Copper ESEEM and HYSCORE through ultra-wideband chirp EPR spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Segawa, Takuya F.; Doll, Andrin; Pribitzer, Stephan

2015-07-28

The main limitation of pulse electron paramagnetic resonance (EPR) spectroscopy is its narrow excitation bandwidth. Ultra-wideband (UWB) excitation with frequency-swept chirp pulses over several hundreds of megahertz overcomes this drawback. This allows to excite electron spin echo envelope modulation (ESEEM) from paramagnetic copper centers in crystals, whereas up to now, only ESEEM of ligand nuclei like protons or nitrogens at lower frequencies could be detected. ESEEM spectra are recorded as two-dimensional correlation experiments, since the full digitization of the electron spin echo provides an additional Fourier transform EPR dimension. Thus, UWB hyperfine-sublevel correlation experiments generate a novel three-dimensional EPR-correlated nuclearmore » modulation spectrum.« less

Femtosecond ultrasonic spectroscopy using a piezoelectric nanolayer: Hypersound attenuation in vitreous silica films

NASA Astrophysics Data System (ADS)

Wen, Yu-Chieh; Guol, Shi-Hao; Chen, Hung-Pin; Sheu, Jinn-Kong; Sun, Chi-Kuang

2011-08-01

We report ultra-broadband ultrasonic spectroscopy with an impedance-matched piezoelectric nanolayer, which enables optical generation and detection of a 730-fs acoustic pulse (the width of ten lattice constants). The bandwidth improvement facilitates THz laser ultrasonics to bridge the spectral gap between inelastic light and x-ray scatterings (0.1-1 THz) in the studies of lattice dynamics. As a demonstration, this method is applied to measure sound attenuation α in a vitreous SiO2 thin film. Our results extend the existing low-frequency data obtained by ultrasonic-based and light scattering methods and also show a α∝ f2 behavior for frequencies f up to 650 GHz.

Reactive hydroxyl radical-driven oral bacterial inactivation by radio frequency atmospheric plasma

NASA Astrophysics Data System (ADS)

Kang, Sung Kil; Choi, Myeong Yeol; Koo, Il Gyo; Kim, Paul Y.; Kim, Yoonsun; Kim, Gon Jun; Mohamed, Abdel-Aleam H.; Collins, George J.; Lee, Jae Koo

2011-04-01

We demonstrated bacterial (Streptococcus mutans) inactivation by a radio frequency power driven atmospheric pressure plasma torch with H2O2 entrained in the feedstock gas. Optical emission spectroscopy identified substantial excited state •OH generation inside the plasma and relative •OH formation was verified by optical absorption. The bacterial inactivation rate increased with increasing •OH generation and reached a maximum 5-log10 reduction with 0.6% H2O2 vapor. Generation of large amounts of toxic ozone is drawback of plasma bacterial inactivation, thus it is significant that the ozone concentration falls within recommended safe allowable levels with addition of H2O2 vapor to the plasma.

Vibrational sum-frequency generation spectroscopy of lipid bilayers at repetition rates up to 100 kHz

NASA Astrophysics Data System (ADS)

Yesudas, Freeda; Mero, Mark; Kneipp, Janina; Heiner, Zsuzsanna

2018-03-01

Broadband vibrational sum-frequency generation (BB-VSFG) spectroscopy has become a well-established surface analytical tool capable of identifying the orientation and structure of molecular layers. A straightforward way to boost the sensitivity of the technique could be to increase the laser repetition rate beyond that of standard BB-VSFG spectrometers, which rely on Ti:sapphire lasers operating at repetition rates of 1-5 kHz. Nevertheless, possible thermally induced artifacts in the vibrational spectra due to higher laser average powers are unexplored. Here, we discuss laser power induced temperature accumulation effects that distort the BB-VSFG spectra of 1,2-diacyl-sn-glycero-3-phosphocholine at an interface between two transparent phases at repetition rates of 5, 10, 50, and 100 kHz at constant pulse energy. No heat-induced distortions were found in the spectra, suggesting that the increase in the laser repetition rate provides a feasible route to an improved signal-to-noise ratio or shorter data acquisition times in BB-VSFG spectroscopy for thin films on transparent substrates. The results have implications for future BB-VSFG spectrometers pushing the detection limit for molecular layers with low surface coverage.

Mode-Locked Multichromatic X-Rays in a Seeded Free-Electron Laser for Single-Shot X-Ray Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiang, Dao; Ding, Yuantao; Raubenheimer, Tor

2012-05-10

We present the promise of generating gigawatt mode-locked multichromatic x rays in a seeded free-electron laser (FEL). We show that, by using a laser to imprint periodic modulation in electron beam phase space, a single-frequency coherent seed can be amplified and further translated to a mode-locked multichromatic output in an FEL. With this configuration the FEL output consists of a train of mode-locked ultrashort pulses which span a wide frequency gap with a series of equally spaced sharp lines. These gigawatt multichromatic x rays may potentially allow one to explore the structure and dynamics of a large number of atomicmore » states simultaneously. The feasibility of generating mode-locked x rays ranging from carbon K edge ({approx}284 eV) to copper L{sub 3} edge ({approx}931 eV) is confirmed with numerical simulation using the realistic parameters of the linac coherent light source (LCLS) and LCLS-II. We anticipate that the mode-locked multichromatic x rays in FELs may open up new opportunities in x-ray spectroscopy (i.e. resonant inelastic x-ray scattering, time-resolved scattering and spectroscopy, etc.).« less

Interfacial structure of soft matter probed by SFG spectroscopy.

PubMed

Ye, Shen; Tong, Yujin; Ge, Aimin; Qiao, Lin; Davies, Paul B

2014-10-01

Sum frequency generation (SFG) vibrational spectroscopy, an interface-specific technique in contrast to, for example, attenuated total reflectance spectroscopy, which is only interface sensitive, has been employed to investigate the surface and interface structure of soft matter on a molecular scale. The experimental arrangement required to carry out SFG spectroscopy, with particular reference to soft matter, and the analytical methods developed to interpret the spectra are described. The elucidation of the interfacial structure of soft matter systems is an essential prerequisite in order to understand and eventually control the surface properties of these important functional materials. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Linear and nonlinear frequency- and time-domain spectroscopy with multiple frequency combs.

PubMed

Bennett, Kochise; Rouxel, Jeremy R; Mukamel, Shaul

2017-09-07

Two techniques that employ equally spaced trains of optical pulses to map an optical high frequency into a low frequency modulation of the signal that can be detected in real time are compared. The development of phase-stable optical frequency combs has opened up new avenues to metrology and spectroscopy. The ability to generate a series of frequency spikes with precisely controlled separation permits a fast, highly accurate sampling of the material response. Recently, pairs of frequency combs with slightly different repetition rates have been utilized to down-convert material susceptibilities from the optical to microwave regime where they can be recorded in real time. We show how this one-dimensional dual comb technique can be extended to multiple dimensions by using several combs. We demonstrate how nonlinear susceptibilities can be quickly acquired using this technique. In a second class of techniques, sequences of ultrafast mode locked laser pulses are used to recover pathways of interactions contributing to nonlinear susceptibilities by using a photo-acoustic modulation varying along the sequences. We show that these techniques can be viewed as a time-domain analog of the multiple frequency comb scheme.

Adaptive sampling dual terahertz comb spectroscopy using dual free-running femtosecond lasers.

PubMed

Yasui, Takeshi; Ichikawa, Ryuji; Hsieh, Yi-Da; Hayashi, Kenta; Cahyadi, Harsono; Hindle, Francis; Sakaguchi, Yoshiyuki; Iwata, Tetsuo; Mizutani, Yasuhiro; Yamamoto, Hirotsugu; Minoshima, Kaoru; Inaba, Hajime

2015-06-02

Terahertz (THz) dual comb spectroscopy (DCS) is a promising method for high-accuracy, high-resolution, broadband THz spectroscopy because the mode-resolved THz comb spectrum includes both broadband THz radiation and narrow-line CW-THz radiation characteristics. In addition, all frequency modes of a THz comb can be phase-locked to a microwave frequency standard, providing excellent traceability. However, the need for stabilization of dual femtosecond lasers has often hindered its wide use. To overcome this limitation, here we have demonstrated adaptive-sampling THz-DCS, allowing the use of free-running femtosecond lasers. To correct the fluctuation of the time and frequency scales caused by the laser timing jitter, an adaptive sampling clock is generated by dual THz-comb-referenced spectrum analysers and is used for a timing clock signal in a data acquisition board. The results not only indicated the successful implementation of THz-DCS with free-running lasers but also showed that this configuration outperforms standard THz-DCS with stabilized lasers due to the slight jitter remained in the stabilized lasers.

Adaptive sampling dual terahertz comb spectroscopy using dual free-running femtosecond lasers

PubMed Central

Yasui, Takeshi; Ichikawa, Ryuji; Hsieh, Yi-Da; Hayashi, Kenta; Cahyadi, Harsono; Hindle, Francis; Sakaguchi, Yoshiyuki; Iwata, Tetsuo; Mizutani, Yasuhiro; Yamamoto, Hirotsugu; Minoshima, Kaoru; Inaba, Hajime

2015-01-01

Terahertz (THz) dual comb spectroscopy (DCS) is a promising method for high-accuracy, high-resolution, broadband THz spectroscopy because the mode-resolved THz comb spectrum includes both broadband THz radiation and narrow-line CW-THz radiation characteristics. In addition, all frequency modes of a THz comb can be phase-locked to a microwave frequency standard, providing excellent traceability. However, the need for stabilization of dual femtosecond lasers has often hindered its wide use. To overcome this limitation, here we have demonstrated adaptive-sampling THz-DCS, allowing the use of free-running femtosecond lasers. To correct the fluctuation of the time and frequency scales caused by the laser timing jitter, an adaptive sampling clock is generated by dual THz-comb-referenced spectrum analysers and is used for a timing clock signal in a data acquisition board. The results not only indicated the successful implementation of THz-DCS with free-running lasers but also showed that this configuration outperforms standard THz-DCS with stabilized lasers due to the slight jitter remained in the stabilized lasers. PMID:26035687

A compact frequency stabilized telecom laser diode for space applications

NASA Astrophysics Data System (ADS)

Philippe, C.; Holleville, D.; Le Targat, R.; Wolf, P.; Leveque, T.; Le Goff, R.; Martaud, E.; Acef, O.

2017-09-01

We report on a Telecom laser diode (LD) frequency stabilization to a narrow iodine hyperfine line in the green range, after frequency tripling process using fibered nonlinear waveguide PPLN crystals. We have generated up to 300 mW optical power in the green range ( 514 nm) from 800 mW of infrared power ( 1542 nm), corresponding to a nonlinear conversion efficiency h = P3?/P? 36%. Less than 10 mW of the generated green power are used for Doppler-free spectroscopy of 127I2 molecular iodine, and -therefore- for the frequency stabilization purpose. The frequency tripling optical setup is very compact (< 5 l), fully fibered, and could operate over the full C-band of the Telecom range (1530 nm - 1565 nm). Several thousands of hyperfine iodine lines may thus be interrogated in the 510 nm - 521 nm range. We build up an optical bench used at first in free space configuration, using the well-known modulation transfer spectroscopy technique (MTS), in order to test the potential of this new frequency standard based on the couple "1.5 ?m laser / iodine molecule". We have already demonstrated a preliminary frequency stability of 4.8 x 10-14 ? -1/2 with a minimum value of 6 x 10-15 reached after 50 s of integration time, conferred to a laser diode operating at 1542.1 nm. We focus now our efforts to expand the frequency stability to a longer integration time in order to meet requirements of many space experiments, such earth gravity missions, inters satellites links or space to ground communications. Furthermore, we investigate the potential of a new approach based on frequency modulation technique (FM), associated to a 3rd harmonic detection of iodine lines to increase the compactness of the optical setup.

Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods.

PubMed

Barnette, Anna L; Lee, Christopher; Bradley, Laura C; Schreiner, Edward P; Park, Yong Bum; Shin, Heenae; Cosgrove, Daniel J; Park, Sunkyu; Kim, Seong H

2012-07-01

The non-centrosymmetry requirement of sum frequency generation (SFG) vibration spectroscopy allows the detection and quantification of crystalline cellulose in lignocellulose biomass without spectral interferences from hemicelluloses and lignin. This paper shows a correlation between the amount of crystalline cellulose in biomass and the SFG signal intensity. Model biomass samples were prepared by mixing commercially available cellulose, xylan, and lignin to defined concentrations. The SFG signal intensity was found sensitive to a wide range of crystallinity, but varied non-linearly with the mass fraction of cellulose in the samples. This might be due to the matrix effects such as light scattering and absorption by xylan and lignin, as well as the non-linear density dependence of the SFG process itself. Comparison with other techniques such as XRD, FT-Raman, FT-IR and NMR demonstrate that SFG can be a complementary and sensitive tool to assess crystalline cellulose in biomass. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues

NASA Astrophysics Data System (ADS)

Wang, Hong-Fei

2016-12-01

Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there have been many progresses in the development of methodology and instrumentation in the SFG-VS toolbox that have significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.

Investigations of coherent anti-Stokes Raman spectroscopy /CARS/ for combustion diagnostics

NASA Technical Reports Server (NTRS)

Eckbreth, A. C.; Hall, R. J.; Shirley, J. A.

1979-01-01

Investigations of coherent anti-Stokes Raman spectroscopy (CARS) in a variety of flames are presented. Thermometry has received the primary emphasis in these studies, but species spectral and sensitivity studies will also be described. CARS is generated by mixing a 10 pps, frequency-doubled neodymium 'pump' laser with a spectrally broadband, laser-pumped, Stokes-shifted dye laser. This approach obviates the requirement to frequency scan the dye laser and generates the entire CARS spectrum with each pulse permitting, in principle, instantaneous measurements of medium properties. CARS spectra of N2, CO, O2, H2O, CO2 and CH4 in flames will be presented. In general these spectra exhibit very good agreement with computer synthesized spectra and permit measurements of temperature and species concentration. To illustrate the applicability of CARS to practical combustion diagnostics, CARS signatures from N2 have been employed to map the temperature field throughout a small, luminous, highly sooting propane diffusion flame

Hyperfine-resolved 3.4-{mu}m spectroscopy of CH{sub 3}I with a widely tunable difference frequency generation source and a cavity-enhanced cell: A case study of a local Coriolis interaction between the v{sub 1}=1 and (v{sub 2},v{sub 6}{sup l})=(1,2{sup 2}) states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okubo, Sho; Nakayama, Hirotaka; Sasada, Hiroyuki

Saturated absorption spectra of the {nu}{sub 1} fundamental band of CH{sub 3}I are recorded with a cavity-enhanced cell and a tunable difference frequency generation source having an 86-cm{sup -1} range. The recorded spectral lines are 250 kHz wide, and most of them are resolved into the individual hyperfine components. The Coriolis interaction between the v{sub 1}=1 and (v{sub 2},v{sub 6}{sup l})=(1,2{sup 2}) states locally perturbing the hyperfine structures is analyzed to yield the Coriolis and hyperfine coupling constants with uncertainties similar to those in typical microwave spectroscopy. The spectrometer has demonstrated the potential for precisely determining the energy structure inmore » the vibrational excited states.« less

Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hong-Fei

Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there has been significant progress in the development of methodology and instrumentation in the SFG-VS toolbox that has significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, somemore » of the controversial issues that have been puzzling the community are to be discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.« less

Mid-infrared optical frequency combs at 2.5 μm based on crystalline microresonators

PubMed Central

Wang, C. Y.; Herr, T.; Del’Haye, P.; Schliesser, A.; Hofer, J.; Holzwarth, R.; Hänsch, T. W.; Picqué, N.; Kippenberg, T. J.

2013-01-01

The mid-infrared spectral range (λ~2–20 μm) is of particular importance as many molecules exhibit strong vibrational fingerprints in this region. Optical frequency combs—broadband optical sources consisting of equally spaced and mutually coherent sharp lines—are creating new opportunities for advanced spectroscopy. Here we demonstrate a novel approach to create mid-infrared optical frequency combs via four-wave mixing in a continuous-wave pumped ultra-high Q crystalline microresonator made of magnesium fluoride. Careful choice of the resonator material and design made it possible to generate a broadband, low-phase noise Kerr comb at λ=2.5 μm spanning 200 nm (≈10 THz) with a line spacing of 100 GHz. With its distinguishing features of compactness, efficient conversion, large mode spacing and high power per comb line, this novel frequency comb source holds promise for new approaches to molecular spectroscopy and is suitable to be extended further into the mid-infrared. PMID:23299895

Vibrational spectral signatures of crystalline cellulose using high resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS)

DOE PAGES

Zhang, Libing; Lu, Zhou; Velarde, Luis; ...

2015-03-03

Both the C–H and O–H region spectra of crystalline cellulose were studied using the sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) for the first time. The resolution of HR-BB-SFG-VS is about 10-times better than conventional scanning SFG-VS and has the capability of measuring the intrinsic spectral lineshape and revealing many more spectral details. With HR-BB-SFG-VS, we found that in cellulose samples from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the O–H region were unique for the two allomorphs, i.e. Iα and Iβ, while the spectral signaturesmore » in the C–H regions varied in all samples examined. Even though the origin of the different spectral signatures of the crystalline cellulose in the O–H and C–H vibrational frequency regions are yet to be correlated to the structure of cellulose, these results lead to new spectroscopic methods and opportunities to classify and to understand the basic crystalline structures, as well as variations in polymorphism of the crystalline cellulose.« less

Vibrational spectral signatures of crystalline cellulose using high resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Libing; Lu, Zhou; Velarde, Luis

Both the C–H and O–H region spectra of crystalline cellulose were studied using the sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) for the first time. The resolution of HR-BB-SFG-VS is about 10-times better than conventional scanning SFG-VS and has the capability of measuring the intrinsic spectral lineshape and revealing many more spectral details. With HR-BB-SFG-VS, we found that in cellulose samples from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the O–H region were unique for the two allomorphs, i.e. Iα and Iβ, while the spectral signaturesmore » in the C–H regions varied in all samples examined. Even though the origin of the different spectral signatures of the crystalline cellulose in the O–H and C–H vibrational frequency regions are yet to be correlated to the structure of cellulose, these results lead to new spectroscopic methods and opportunities to classify and to understand the basic crystalline structures, as well as variations in polymorphism of the crystalline cellulose.« less

Mid-infrared frequency comb via coherent dispersive wave generation in silicon nitride nanophotonic waveguides

NASA Astrophysics Data System (ADS)

Guo, Hairun; Herkommer, Clemens; Billat, Adrien; Grassani, Davide; Zhang, Chuankun; Pfeiffer, Martin H. P.; Weng, Wenle; Brès, Camille-Sophie; Kippenberg, Tobias J.

2018-06-01

Mid-infrared optical frequency combs are of significant interest for molecular spectroscopy due to the large absorption of molecular vibrational modes on the one hand, and the ability to implement superior comb-based spectroscopic modalities with increased speed, sensitivity and precision on the other hand. Here, we demonstrate a simple, yet effective, method for the direct generation of mid-infrared optical frequency combs in the region from 2.5 to 4.0 μm (that is, 2,500-4,000 cm-1), covering a large fraction of the functional group region, from a conventional and compact erbium-fibre-based femtosecond laser in the telecommunication band (that is, 1.55 μm). The wavelength conversion is based on dispersive wave generation within the supercontinuum process in an unprecedented large-cross-section silicon nitride (Si3N4) waveguide with the dispersion lithographically engineered. The long-wavelength dispersive wave can perform as a mid-infrared frequency comb, whose coherence is demonstrated via optical heterodyne measurements. Such an approach can be considered as an alternative option to mid-infrared frequency comb generation. Moreover, it has the potential to realize compact dual-comb spectrometers. The generated combs also have a fine teeth-spacing, making them suitable for gas-phase analysis.

Very high frequency spectroscopy and tuning of a single-cooper-pair transistor with an on-chip generator.

PubMed

Billangeon, P-M; Pierre, F; Bouchiat, H; Deblock, R

2007-03-23

A single-Cooper-pair transistor (SCPT) is coupled capacitively to a voltage biased Josephson junction, used as a high-frequency generator. Thanks to the high energy of photons generated by the Josephson junction, transitions between energy levels, not limited to the first two levels, were induced and the effect of this irradiation on the dc Josephson current of the SCPT was measured. The phase and gate bias dependence of energy levels of the SCPT at high energy is probed. Because the energies of photons can be higher than the superconducting gap we can induce not only transfer of Cooper pairs but also transfer of quasiparticles through the island of the SCPT, thus controlling the poisoning of the SCPT. This can both decrease and increase the average Josephson energy of the SCPT: its supercurrent is then controlled by high-frequency irradiation.

Terahertz technology for imaging and spectroscopy

NASA Astrophysics Data System (ADS)

Crowe, T. W.; Porterfield, D. W.; Hesler, J. L.; Bishop, W. L.; Kurtz, D. S.; Hui, K.

2006-05-01

The terahertz region of the electromagnetic spectrum has unique properties that make it especially useful for imaging and spectroscopic detection of concealed weapons, explosives and chemical and biological materials. However, terahertz energy is difficult to generate and detect, and this has led to a technology gap in this frequency band. Nonlinear diodes can be used to bridge this gap by translating the functionality achieved at microwave frequencies to the terahertz band. Basic building blocks include low-noise mixers, frequency multipliers, sideband generators and direct detectors. These terahertz components rely on planar Schottky diodes and recently developed integrated diode circuits make them easier to assemble and more robust. The new generation of terahertz sources and receivers requires no mechanical tuning, yet achieves high efficiency and broad bandwidth. This paper reviews the basic design of terahertz transmitters and receivers, with special emphasis on the recent development of systems that are compact, easy to use and have excellent performance.

Mid-infrared trace gas detection using continuous-wave difference frequency generation in periodically poled RbTiOAsO4

NASA Technical Reports Server (NTRS)

Chen, W.; Mouret, G.; Boucher, D.; Tittel, F. K.

2001-01-01

A tunable mid-infrared continuous-wave (cw) spectroscopic source in the 3.4-4.5 micrometers region is reported, based on difference frequency generation (DFG) in a quasi-phase-matched periodically poled RbTiOAsO4 (PPRTA) crystal. DFG power levels of 10 microW were generated at approximately 4 micrometers in a 20-mm long PPRTA crystal by mixing two cw single-frequency Ti:Al2O3 lasers operating near 713 nm and 871 nm, respectively, using a laser pump power of 300 mW. A quasi-phase-matched infrared wavelength-tuning bandwidth (FWHM) of 12 cm-1 and a temperature tuning rate of 1.02 cm-1/degree C were achieved. Experimental details regarding the feasibility of trace gas detection based on absorption spectroscopy of CO2 in ambient air using this DFG radiation source are also described.

Transport limited interfacial carrier relaxation in a double-layer device investigated by time-resolved second harmonic generation and impedance spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Le; Taguchi, Dai; Li, Jun; Manaka, Takaaki; Iwamoto, Mitsumasa

2011-02-01

The interfacial carrier relaxation in an indium tin oxide/polyimide/pentacene/Au double-layer device was studied in both time and frequency domains by using time-resolved second harmonic generation (TR-SHG) and impedance spectroscopy (IS), respectively. Although both hole and electron injection into the pentacene layer and their accumulation at the pentacene/polyimide interface were revealed in TR-SHG, it was only observed in IS under the hole injection condition. The "contradiction" between the two methods for the same carrier relaxation process was explained on the basis of a model, transport limited interfacial carrier relaxation, in which the quasistatic state governs the one-directional carrier transport.

Method for conducting nonlinear electrochemical impedance spectroscopy

DOEpatents

Adler, Stuart B.; Wilson, Jamie R.; Huff, Shawn L.; Schwartz, Daniel T.

2015-06-02

A method for conducting nonlinear electrochemical impedance spectroscopy. The method includes quantifying the nonlinear response of an electrochemical system by measuring higher-order current or voltage harmonics generated by moderate-amplitude sinusoidal current or voltage perturbations. The method involves acquisition of the response signal followed by time apodization and fast Fourier transformation of the data into the frequency domain, where the magnitude and phase of each harmonic signal can be readily quantified. The method can be implemented on a computer as a software program.

Support effects in catalysis studied by in-situ sum frequency generation vibrational spectroscopy and in-situ x-ray spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, Griffin John

Here, kinetic measurements are paired with in-situ spectroscopic characterization tools to investigate colloidally based, supported Pt catalytic model systems in order to elucidate the mechanisms by which metal and support work in tandem to dictate activity and selectivity. The results demonstrate oxide support materials, while inactive in absence of Pt nanoparticles, possess unique active sites for the selective conversion of gas phase molecules when paired with an active metal catalyst.

Dual comb generation from a mode-locked fiber laser with orthogonally polarized interlaced pulses.

PubMed

Akosman, Ahmet E; Sander, Michelle Y

2017-08-07

Ultra-high precision dual-comb spectroscopy traditionally requires two mode-locked, fully stabilized lasers with complex feedback electronics. We present a novel mode-locked operation regime in a thulium-holmium co-doped fiber laser, a frequency-halved state with orthogonally polarized interlaced pulses, for dual comb generation from a single source. In a linear fiber laser cavity, an ultrafast pulse train composed of co-generated, equal intensity and orthogonally polarized consecutive pulses at half of the fundamental repetition rate is demonstrated based on vector solitons. Upon optical interference of the orthogonally polarized pulse trains, two stable microwave RF beat combs are formed, effectively down-converting the optical properties into the microwave regime. These co-generated, dual polarization interlaced pulse trains, from one all-fiber laser configuration with common mode suppression, thus provide an attractive compact source for dual-comb spectroscopy, optical metrology and polarization entanglement measurements.

Evaluating the coherence and time-domain profile of quantum cascade laser frequency combs

DOE PAGES

Burghoff, David; Yang, Yang; Hayton, Darren J.; ...

2015-01-01

Recently, much attention has been focused on the generation of optical frequency combs from quantum cascade lasers. We discuss how fast detectors can be used to demonstrate the mutual coherence of such combs, and present an inequality that can be used to quantitatively evaluate their performance. We discuss several technical issues related to shifted wave interference Fourier Transform spectroscopy (SWIFTS), and show how such measurements can be used to elucidate the time-domain properties of such combs, showing that they can possess signatures of both frequency-modulation and amplitude-modulation.

Search for inversion splitting in the 3ν2 band of phosphine

NASA Astrophysics Data System (ADS)

Okuda, Shoko; Sasada, Hiroyuki

2018-04-01

Sub-Doppler resolution spectroscopy of the 3ν2 band of phosphine has been carried out using a difference-frequency-generation source referenced to an optical frequency comb and a cavity-enhanced absorption cell. Three Q-branch transitions are recorded with a linewidth of 150 kHz, but no inversion splitting is observed even though it was predicted 300 kHz in Journal of Chemical Physics, vol. 145, art. No. 091102 (2016). Transition frequencies of six Q-branch transitions have been determined with an uncertainty of 6-16 kHz.

Consensus structures of the Mo(v) sites of sulfite-oxidizing enzymes derived from variable frequency pulsed EPR spectroscopy, isotopic labelling and DFT calculations.

PubMed

Enemark, John H

2017-10-10

Sulfite-oxidizing enzymes from eukaryotes and prokaryotes have five-coordinate distorted square-pyramidal coordination about the molybdenum atom. The paramagnetic Mo(v) state is easily generated, and over the years four distinct CW EPR spectra have been identified, depending upon enzyme source and the reaction conditions, namely high and low pH (hpH and lpH), phosphate inhibited (P i ) and sulfite (or blocked). Extensive studies of these paramagnetic forms of sulfite-oxidizing enzymes using variable frequency pulsed electron spin echo (ESE) spectroscopy, isotopic labeling and density functional theory (DFT) calculations have led to the consensus structures that are described here. Errors in some of the previously proposed structures are corrected.

Generation and multi-octave shaping of mid-infrared intense single-cycle pulses

NASA Astrophysics Data System (ADS)

Krogen, Peter; Suchowski, Haim; Liang, Houkun; Flemens, Noah; Hong, Kyung-Han; Kärtner, Franz X.; Moses, Jeffrey

2017-03-01

The generation of intense mid-infrared (mid-IR) optical pulses with customizable shape and spectra spanning a multiple-octave range of vibrational frequencies is an elusive technological capability. While some recent approaches to mid-IR supercontinuum generation—such as filamentation, multicolour four-wave-mixing and optical rectification—have successfully generated broad spectra, no process has been identified for achieving complex pulse shaping at the generation step. The adiabatic frequency converter allows for a one-to-one transfer of spectral phase through nonlinear frequency conversion over a larger-than-octave-spanning range and with an overall linear phase transfer function. Here, we show that we can convert shaped near-infrared (near-IR) pulses to shaped, energetic, multi-octave-spanning mid-IR pulses lasting only 1.2 optical cycles, and extendable to the sub-cycle regime. We expect this capability to enable a new class of precisely controlled nonlinear interactions in the mid-IR spectral range, from nonlinear vibrational spectroscopy to strong light-matter interactions and single-shot remote sensing.

The Physics of Ultrabroadband Frequency Comb Generation and Optimized Combs for Measurements in Fundamental Physics

DTIC Science & Technology

2016-07-02

great potential of chalcogenide microwires for applications in the mid-IR ranging from absorption spectroscopy to entangled photon pairs generation...modulation instability) gain. Stochastic nonlinear Schrödinger equation simulations were shown to be in very good agreement with experiment. This...as the seed coherence decreases. Stochastic nonlinear Schrödinger equation simulations of spectral and noise properties are in excellent agreement with

Electric and dielectric behavior of copper-chromium layered double hydroxide intercalated with dodecyl sulfate anions using impedance spectroscopy

NASA Astrophysics Data System (ADS)

Elhatimi, Wafaa; Bouragba, Fatima Zahra; Lahkale, Redouane; Sadik, Rachid; Lebbar, Nacira; Siniti, Mostapha; Sabbar, Elmouloudi

2018-05-01

The Cu2Cr-DS-LDH hybrid was successfully prepared by the anion exchange method at room temperature. The structure, the chemical composition and the physico-chemical properties of the sample were determined using powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and inductively coupled plasma (ICP). In this work, the electrical and dielectric properties investigated are determined using impedance spectroscopy (IS) in a frequency range of 1 Hz to 1 MHz. Indeed, the Nyquist diagram modelized by an electrical equivalent circuit showed three contributions attributed respectively to the polarization of grains, grains boundaries and interface electrode-sample. This modelization allowed us to determine the intrinsic electrical parameters of the hybrid (resistance, pseudo-capacitance and relaxation time). The presence of the non-Debye relaxation phenomena was confirmed by the frequency analysis of impedance. Moreover, the evolution of the alternating current conductivity (σac) studied obeys the double power law of Jonscher. The ionic conduction of this material was generated through a jump movement by translation of the charge carriers. As for the dielectric behavior of the material, the evolution of dielectric constant as a function of frequency shows relatively high values in a frequency range between 10 Hz and 1 KHz. The low values of the loss tangent obtained in this frequency zone can valorize this LDH hybrid.

Plasmon-Induced Magnetic Resonance Enhanced Raman Spectroscopy.

PubMed

Chen, Shu; Zhang, Yuejiao; Shih, Tien-Mo; Yang, Weimin; Hu, Shu; Hu, Xiaoyan; Li, Jianfeng; Ren, Bin; Mao, Bingwei; Yang, Zhilin; Tian, Zhongqun

2018-04-11

Plasmon-induced magnetic resonance has shown great potentials in optical metamaterials, chemical (bio)-sensing, and surface-enhanced spectroscopies. Here, we have theoretically and experimentally revealed (1) a correspondence of the strongest near-field response to the far-field scattering valley and (2) a significant improvement in Raman signals of probing molecules by the plasmon-induced magnetic resonance. These revelations are accomplished by designing a simple and practical metallic nanoparticle-film plasmonic system that generates magnetic resonances at visible-near-infrared frequencies. Our work may provide new insights for understanding the enhancement mechanism of various plasmon-enhanced spectroscopies and also helps further explore light-matter interactions at the nanoscale.

Intensity enhancement of vibrational sum frequency generation by gap-mode plasmon resonance

NASA Astrophysics Data System (ADS)

Okuno, Masanari; Tokimoto, Taichi; Eguchi, Miharu; Kano, Hideaki; Ishibashi, Taka-aki

2015-10-01

A metal sphere-plane structure consisting of gold nanoparticles, p-methylbenzenethiol and a gold substrate was measured by vibrational sum frequency generation spectroscopy with four excitation wavelengths, 630, 680, 720, and 780 nm. The enhancement factors of Raman signals were estimated to be 250 and 104 for the 532 and 647 nm excitation. Contrastingly, we found that the enhancements of VSFG signals were much smaller, a factor of 5 at maximum. We speculate that the small enhancement factor of VSFG signals is due to the coherent nature of the VSFG process or the extinction of the infrared laser by the gold nanoparticles.

A Two-Color Fourier Transform Mm-Wave Spectrometer for Gas Analysis Operating from 260-295 GHZ

NASA Astrophysics Data System (ADS)

Steber, Amanda L.; Harris, Brent J.; Lehmann, Kevin K.; Pate, Brooks H.

2013-06-01

We have designed a two-color mm-wave spectrometer for Fourier transform mm-wave spectroscopy that uses consumer level components for the tunable synthesizers, digital control of the pulse modulators, and digitization of the coherent free induction decay (FID). The excitation pulses are generated using an x24 active multiplier chain (AMC) that produces a peak power of 30 mW. The microwave input to the AMC is generated in a frequency up conversion circuit that accepts a microwave input frequency from about 2-4 GHz. This circuit also generates the input to the mm-wave subhamonic mixer that creates the local oscillator from a separate 2-4 GHz microwave input. Excitation pulses at two independently tunable frequencies are generated using a dual-channel source based on a low-cost, wideband synthesizer integrated circuit (Valon Technology Model 5008). The outputs of the synthesizer are pulse modulated using a PIN diode switch that is driven using the arbitrary waveform generator (AWG) output of a USB-controlled high-speed digitizer / arbitrary waveform generator combination unit (Tie Pie HS-5 530 XM). The two pulses are combined using a Wilkinson power divider before input to the up conversion circuit. The FID frequency is down converted in a two-stage mixing process to 65 MHz. The two LO frequencies used in the receiver are provided by a second Valon 5008. The FID is digitized at 200 MSamples/s using the 12-bit Tie Pie digitizer. The digital oscilloscope (and its AWG channel) and the two synthesizers use a 10 MHz reference signal from a Rubidium clock to permit time-domain signal averaging. A key feature of the digital oscilloscope is its deep memory of 32 Mpts (complemented by the 64 Mpt memory in the 240 MS/s AWG). This makes it possible to perform several one- and two-color coherent measurements, including pulse echoes and double-resonance spectroscopy, in a single "readout" experiment to speed the analysis of mm-wave rotational spectra. The spectrometer sensitivity and frequency accuracy are illustrated by high-speed measurements of OCS rotational transitions for low-abundance isotopes. Examples of pulse echo measurements to determine the collisional relaxation rate and two-color double-resonance measurements to confirm the presence of a molecular species will be illustrated using OCS as the room-temperature gas sample.

Phase transition behaviors of the supported DPPC bilayer investigated by sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM).

PubMed

Wu, Heng-Liang; Tong, Yujin; Peng, Qiling; Li, Na; Ye, Shen

2016-01-21

The phase transition behaviors of a supported bilayer of dipalmitoylphosphatidyl-choline (DPPC) have been systematically evaluated by in situ sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM). By using an asymmetric bilayer composed of per-deuterated and per-protonated monolayers, i.e., DPPC-d75/DPPC and a symmetric bilayer of DPPC/DPPC, we were able to probe the molecular structural changes during the phase transition process of the lipid bilayer by SFG spectroscopy. It was found that the DPPC bilayer is sequentially melted from the top (adjacent to the solution) to bottom leaflet (adjacent to the substrate) over a wide temperature range. The conformational ordering of the supported bilayer does not decrease (even slightly increases) during the phase transition process. The conformational defects in the bilayer can be removed after the complete melting process. The phase transition enthalpy for the bottom leaflet was found to be approximately three times greater than that for the top leaflet, indicating a strong interaction of the lipids with the substrate. The present SFG and AFM observations revealed similar temperature dependent profiles. Based on these results, the temperature-induced structural changes in the supported lipid bilayer during its phase transition process are discussed in comparison with previous studies.

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

DOE PAGES

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.; ...

2017-05-12

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

Characterization of starch polymorphic structures using vibrational sum frequency generation spectroscopy.

PubMed

Kong, Lingyan; Lee, Christopher; Kim, Seong H; Ziegler, Gregory R

2014-02-20

The polymorphic structures of starch were characterized with vibrational sum frequency generation (SFG) spectroscopy. The noncentrosymmetry requirement of SFG spectroscopy allows for the detection of the ordered domains without spectral interferences from the amorphous phase and also the distinction of the symmetric elements among crystalline polymorphs. The V-type amylose was SFG-inactive due to the antiparallel packing of single helices in crystal unit cells, whereas the A- and B-type starches showed strong SFG peaks at 2904 cm(-1) and 2952-2968 cm(-1), which were assigned to CH stretching of the axial methine group in the ring and CH2 stretching of the exocyclic CH2OH side group, respectively. The CH2/CH intensity ratios of the A- and B-type starches are significantly different, indicating that the conformation of hydroxymethyl groups in these two polymorphs may be different. Cyclodextrin inclusion complexes were also analyzed as a comparison to the V-type amylose and showed that the head-to-tail and head-to-head stacking patterns of cyclodextrin molecules govern their SFG signals and peak positions. Although the molecular packing is different between V-type amylose and cyclodextrin inclusion complexes, both crystals show the annihilation of SFG signals when the functional group dipoles are arranged pointing in opposite directions.

Freezing and melting of salt hydrates next to solid surfaces probed by infrared-visible sum frequency generation spectroscopy.

PubMed

Anim-Danso, Emmanuel; Zhang, Yu; Dhinojwala, Ali

2013-06-12

Understanding the freezing of salt solutions near solid surfaces is important in many scientific fields. Here we use sum frequency generation (SFG) spectroscopy to study the freezing of a NaCl solution next to a sapphire substrate. During cooling we observe two transitions. The first corresponds to segregation of concentrated brine next to the sapphire surface as we cool the system down to the region where ice and brine phases coexist. At this transition, the intensity of the ice-like peak decreases, suggesting the disruption of hydrogen-bonding by sodium ions. The second transition corresponds to the formation of NaCl hydrates with abrupt changes in both the SFG intensity and the sharpness of spectral peaks. The similarity in the position of the SFG peaks with those observed using IR and Raman spectroscopy indicates the formation of NaCl·2H2O crystals next to the sapphire substrate. The melting temperatures of the hydrates are very similar to those reported for bulk NaCl·2H2O. This study enhances our understanding of nucleation and freezing of salt solutions on solid surfaces and the effects of salt ions on the structure of interfacial ice.

Efficient On-chip Optical Microresonator for Optical Comb Generation: Design and Fabrication

NASA Astrophysics Data System (ADS)

Han, Kyunghun

An optical frequency comb is a series of equally spaced frequency components. It has gained much attention since Nobel physics prize was awarded John L. Hall and Theodor W. Hansch for their contribution to the optical frequency comb technique in 2005. The optical frequency comb has been extensively studied because of its precision as a tool for spectroscopy, and is now widely used in bio- and chemical sensors, optical clocks, mode-locked dark pulse generation, soliton generation, and optical communication. Recently, thanks to the developments in nanotechnology, the optical frequency comb generation is made possible at a chip-scale level with microresonators. However, because the threshold power of the optical frequency comb generation is beyond the capability of the on-chip laser source, efficient microresonator is required. Here, we demonstrate an ultra-compact and highly efficient strip-slot direct mode coupler, aiming to achieve slotted silicon microresonator cladded with nonlinear polymer Poly-DDMEBT in SOI platform. As an application of the strip-slot direct mode coupling, a double slot fiber-to-chip edge coupler is demonstrated showing 2 dB insertion loss reduction compared to the conventional single tip edge coupler. For silicon nitride platform, we investigated evanescent wave coupling of microresonator, focusing on bus waveguide geometry optimization. The optimized waveguide width offers an efficient excitation of a fundamental mode in the resonator waveguide. This investigation can benefit low threshold comb generation by enhancing the extinction ratio. We experimentally demonstrated the high Q-factor micro-ring resonator with intrinsic Q of 12.6 million as well as the single FSR comb generation with 63 mW.

Ultrafast fluorescence spectroscopy of biologically relevant chromophores using type II difference frequency generation

NASA Astrophysics Data System (ADS)

Léonard, J.; Gelot, T.; Torgasin, K.; Haacke, S.

2011-01-01

A novel femtosecond fluorescence experiment based on type II difference frequency mixing is demonstrated. This approach is particularly interesting for near-UV emitting biological chromophores like amino acids and nucleotides, as the fluorescence is converted into the spectral range where CCD have their highest quantum efficiencies. The method is implemented with a 5-kHz amplified Ti:Sapphire laser system and first results obtained with 2,5-diphenyloxazole (PPO) in ethanol are reported.

Next generation techniques in the high resolution spectroscopy of biologically relevant molecules.

PubMed

Neill, Justin L; Douglass, Kevin O; Pate, Brooks H; Pratt, David W

2011-04-28

Recent advances in the technology of test and measurement equipment driven by the computer and telecommunications industries have made possible the development of a new broadband, Fourier-transform microwave spectrometer that operates on principles similar to FTNMR. This technique uses a high sample-rate arbitrary waveform generator to construct a phase-locked chirped microwave pulse that gives a linear frequency sweep over a wide frequency range in 1 μs. The chirped pulse efficiently polarizes the molecular sample at all frequencies lying within this band. The subsequent free induction decay of this polarization is measured with a high-speed digitizer and then fast Fourier-transformed to yield a broadband, frequency-resolved rotational spectrum, spanning up to 11.5 GHz and containing lines that are as narrow as 100 kHz. This new technique is called chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. The technique offers the potential to determine the structural and dynamical properties of very large molecules solely from fully resolved pure rotational spectra. FTMW double resonance techniques employing a low-resolution UV laser facilitate an easy assignment of overlapping spectra produced by different conformers in the sample. Of particular interest are the energy landscapes of conformationally flexible molecules of biological importance, including studies of their interaction with solvent and/or other weakly bound molecules. An example is provided from the authors' work on p-methoxyphenethylamine, a neurotransmitter, and its complexes with water.

The Discrete Nature of the Coherent Synchrotron Radiation

NASA Astrophysics Data System (ADS)

Tammaro, Stefano; Pirali, Olivier; Roy, P.; Lampin, Jean François; Ducourneau, Gaël; Cuisset, Arnaud; Hindle, Francis; Mouret, Gaël

2015-06-01

Frequency Combs (FC) have radically changed the landscape of frequency metrology and high-resolution spectroscopy investigations extending tremendously the achievable resolution while increasing signal to noise ratio. Initially developed in the visible and near-IR spectral regions, the use of FC has been expanded to mid-IR, extreme ultra-violet and X-ray. Significant effort is presently dedicated to the generation of FC at THz frequencies. One solution based on converting a stabilized optical frequency comb using a photoconductive terahertz emitter, remains hampered by the low available THz power. Another approach is based on active mode locked THz quantum-cascade-lasers providing intense FC over a relatively limited spectral extension. Alternatively, we show that dense powerful THz FC is generated over one decade of frequency by coherent synchrotron radiation (CSR). In this mode, the entire ring behaves in a similar fashion to a THz resonator wherein electron bunches emit powerful THz pulses quasi-synchronously. The observed FC has been fully characterized and is demonstrated to be offset free. Based on these recorded specifications and a complete review of existing THz frequency comb, a special attention will be paid onto similarities and differences between them. Udem, Th., Holzwarth, H., Hänsch, T. W., Optical frequency metrology. Nature 416, 233-237 (2002) Schliesser, A., Picqué, N., Hänsch, T. W., Mid-infrared frequency combs. Nature Photon. 6, 440 (2012) Zinkstok, R. Th., Witte, S., Ubachs, W., Hogervorst, W., Eikema, K. S. E., Frequency comb laser spectroscopy in the vacuum-ultraviolet region. Physical Review A 73, 061801 (2006) Cavaletto, S. M. et al. Broadband high-resolution X-ray frequency combs. Nature Photon. 8, 520-523 (2014) Tani, M., Matsuura, S., Sakai, K., Nakashima, S. I., Emission characteristics of photoconductive antennas based on low-temperature-grown GaAs and semi-insulating GaAs. Applied Optics 36, 7853-7859 (1997) Burghoff, D. et al. Terahertz laser frequency combs. Nature Photon. 8, 462-467 (2014)

Call for papers for special issue of Journal of Molecular Spectroscopy focusing on "Frequency-comb spectroscopy"

NASA Astrophysics Data System (ADS)

Foltynowicz, Aleksandra; Picqué, Nathalie; Ye, Jun

2018-05-01

Frequency combs are becoming enabling tools for many applications in science and technology, beyond the original purpose of frequency metrology of simple atoms. The precisely evenly spaced narrow lines of a laser frequency comb inspire intriguing approaches to molecular spectroscopy, designed and implemented by a growing community of scientists. Frequency-comb spectroscopy advances the frontiers of molecular physics across the entire electro-magnetic spectrum. Used as frequency rulers, frequency combs enable absolute frequency measurements and precise line shape studies of molecular transitions, for e.g. tests of fundamental physics and improved determination of fundamental constants. As light sources interrogating the molecular samples, they dramatically improve the resolution, precision, sensitivity and acquisition time of broad spectral-bandwidth spectroscopy and open up new opportunities and applications at the leading edge of molecular spectroscopy and sensing.

Phase-locking to a free-space terahertz comb for metrological-grade terahertz lasers.

PubMed

Consolino, L; Taschin, A; Bartolini, P; Bartalini, S; Cancio, P; Tredicucci, A; Beere, H E; Ritchie, D A; Torre, R; Vitiello, M S; De Natale, P

2012-01-01

Optical frequency comb synthesizers have represented a revolutionary approach to frequency metrology, providing a grid of frequency references for any laser emitting within their spectral coverage. Extending the metrological features of optical frequency comb synthesizers to the terahertz domain would be a major breakthrough, due to the widespread range of accessible strategic applications and the availability of stable, high-power and widely tunable sources such as quantum cascade lasers. Here we demonstrate phase-locking of a 2.5 THz quantum cascade laser to a free-space comb, generated in a LiNbO(3) waveguide and covering the 0.1-6 THz frequency range. We show that even a small fraction (<100 nW) of the radiation emitted from the quantum cascade laser is sufficient to generate a beat note suitable for phase-locking to the comb, paving the way to novel metrological-grade terahertz applications, including high-resolution spectroscopy, manipulation of cold molecules, astronomy and telecommunications.

Probing organic field effect transistors in situ during operation using SFG.

PubMed

Ye, Hongke; Abu-Akeel, Ashraf; Huang, Jia; Katz, Howard E; Gracias, David H

2006-05-24

In this communication, we report results obtained using surface-sensitive IR+Visible Sum Frequency Generation (SFG) nonlinear optical spectroscopy on interfaces of organic field effect transistors during operation. We observe remarkable correlations between trends in the surface vibrational spectra and electrical properties of the transistor, with changes in gate voltage (VG). These results suggest that field effects on electronic conduction in thin film organic semiconductor devices are correlated to interfacial nonlinear optical characteristics and point to the possibility of using SFG spectroscopy to monitor electronic properties of OFETs.

Comb-referenced ultra-high sensitivity spectroscopic molecular detection by compact non-linear sources

NASA Astrophysics Data System (ADS)

Cancio, P.; Gagliardi, G.; Galli, I.; Giusfredi, G.; Maddaloni, P.; Malara, P.; Mazzotti, D.; De Natale, P.

2017-11-01

We present a new generation of compact and rugged mid-infrared (MIR) difference-frequency coherent radiation sources referenced to fiber-based optical frequency comb synthesizers (OFCSs). By coupling the MIR radiation to high-finesse optical cavities, high-resolution and high-sensitivity spectroscopy is demonstrated for CH4 and CO2 around 3.3 and 4.5 μm respectively. Finally, the most effective detection schemes for space-craft trace-gas monitoring applications are singled out.

Quantitative Surface Chirality Detection with Sum Frequency Generation Vibrational Spectroscopy: Twin Polarization Angle Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Feng; Xu, Yanyan; Guo, Yuan

2009-12-27

Here we report a novel twin polarization angle (TPA) approach in the quantitative chirality detection with the surface sum-frequency generation vibrational spectroscopy (SFG-VS). Generally, the achiral contribution dominates the surface SFG-VS signal, and the pure chiral signal is usually two or three orders of magnitude smaller. Therefore, it has been difficult to make quantitative detection and analysis of the chiral contributions to the surface SFG- VS signal. In the TPA method, by varying together the polarization angles of the incoming visible light and the sum frequency signal at fixed s or p polarization of the incoming infrared beam, the polarizationmore » dependent SFG signal can give not only direct signature of the chiral contribution in the total SFG-VS signal, but also the accurate measurement of the chiral and achiral components in the surface SFG signal. The general description of the TPA method is presented and the experiment test of the TPA approach is also presented for the SFG-VS from the S- and R-limonene chiral liquid surfaces. The most accurate degree of chiral excess values thus obtained for the 2878 cm⁻¹ spectral peak of the S- and R-limonene liquid surfaces are (23.7±0.4)% and ({25.4±1.3)%, respectively.« less

Spectral assignment and orientational analysis in a vibrational sum frequency generation study of DPPC monolayers at the air/water interface

NASA Astrophysics Data System (ADS)

Feng, Rong-Juan; Li, Xia; Zhang, Zhen; Lu, Zhou; Guo, Yuan

2016-12-01

The interfacial behavior of the benchmark zwitterionic phospholipid molecule dipalmitoylphosphatidylcholine (DPPC) has been extensively investigated by surface-selective vibrational sum frequency generation spectroscopy (VSFG). However, there is still a lack of agreement between various orientational measurements of phospholipid monolayers at the air/water interface, mainly because of the difficulty in assigning congested VSFG features. In this study, polarization-dependent VSFG measurements reveal a frequency shift between the in-plane and out-of-plane antisymmetric stretching modes of the terminal methyl groups in the DPPC alkyl tails, favoring the model of Cs local symmetry rather than the previously assumed C3v symmetry. Further VSFG experiments of isotopically labeled DPPC successfully capture the vibrational signatures of the glycerol backbone. With the newly derived VSFG polarization selection rules for Cs symmetry and the refreshed spectral assignments, the average tilt angles of the alkyl tail groups, choline headgroup, and glycerol backbone of DPPC molecules can all be determined, showing the powerful capability of VSFG spectroscopy in revealing the structural details at interfaces. The VSFG polarization dependence rules and the orientational analysis procedures developed for Cs symmetry in this work are applicable to other bulky molecules in which the methyl group cannot freely rotate, and they therefore have general applications in future VSFG studies.

Observation of ν1+νn combination bands of the HOOO and DOOO radicals using infrared action spectroscopy

NASA Astrophysics Data System (ADS)

Derro, Erika L.; Sechler, Timothy D.; Murray, Craig; Lester, Marsha I.

2008-06-01

Hydrogen trioxy (HOOO) and its deuterated analog (DOOO) have been generated in a supersonic free-jet expansion through association of photolytically generated OH or OD and molecular oxygen. The radicals were detected using infrared action spectroscopy, a highly sensitive double resonance technique. Rotationally resolved spectra of combination bands of HOOO and DOOO comprising one quantum of OH or OD stretch (ν1) and one quantum of a lower frequency mode (ν1+νn where n=3-6), including H/DOO bend (ν3), OOO bend (ν4), central OO stretch (ν5), and H/DOOO torsion (ν6), have been observed and assigned to the trans conformer. All but one of these bands are accompanied by unstructured features which are tentatively assigned to the corresponding vibration of the cis conformer. In total, five additional bands of HOOO and four of DOOO have been recorded and assigned. These data represent the first gas-phase observation of the low-frequency modes of HOOO and DOOO and they are found to differ significantly from previous matrix studies and theoretical predictions. Accurate knowledge of the vibrational frequencies is crucial in assessing thermochemical properties of HOOO and present possible means of detection in the atmosphere.

Strong Field-Induced Frequency Conversion of Laser Radiation in Plasma Plumes: Recent Achievements

PubMed Central

Ganeev, R. A.

2013-01-01

New findings in plasma harmonics studies using strong laser fields are reviewed. We discuss recent achievements in the growth of the efficiency of coherent extreme ultraviolet (XUV) radiation sources based on frequency conversion of the ultrashort pulses in the laser-produced plasmas, which allowed for the spectral and structural studies of matter through the high-order harmonic generation (HHG) spectroscopy. These studies showed that plasma HHG can open new opportunities in many unexpected areas of laser-matter interaction. Besides being considered as an alternative method for generation of coherent XUV radiation, it can be used as a powerful tool for various spectroscopic and analytical applications. PMID:23864818

First-Principles Framework to Compute Sum-Frequency Generation Vibrational Spectra of Semiconductors and Insulators.

PubMed

Wan, Quan; Galli, Giulia

2015-12-11

We present a first-principles framework to compute sum-frequency generation (SFG) vibrational spectra of semiconductors and insulators. The method is based on density functional theory and the use of maximally localized Wannier functions to compute the response to electric fields, and it includes the effect of electric field gradients at surfaces. In addition, it includes quadrupole contributions to SFG spectra, thus enabling the verification of the dipole approximation, whose validity determines the surface specificity of SFG spectroscopy. We compute the SFG spectra of ice I_{h} basal surfaces and identify which spectra components are affected by bulk contributions. Our results are in good agreement with experiments at low temperature.

High frequency resolution terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Sangala, Bagvanth Reddy

2013-12-01

A new method for the high frequency resolution terahertz time-domain spectroscopy is developed based on the characteristic matrix method. This method is useful for studying planar samples or stack of planar samples. The terahertz radiation was generated by optical rectification in a ZnTe crystal and detected by another ZnTe crystal via electro-optic sampling method. In this new characteristic matrix based method, the spectra of the sample and reference waveforms will be modeled by using characteristic matrices. We applied this new method to measure the optical constants of air. The terahertz transmission through the layered systems air-Teflon-air-Quartz-air and Nitrogen gas-Teflon-Nitrogen gas-Quartz-Nitrogen gas was modeled by the characteristic matrix method. A transmission coefficient is derived from these models which was optimized to fit the experimental transmission coefficient to extract the optical constants of air. The optimization of an error function involving the experimental complex transmission coefficient and the theoretical transmission coefficient was performed using patternsearch algorithm of MATLAB. Since this method takes account of the echo waveforms due to reflections in the layered samples, this method allows analysis of longer time-domain waveforms giving rise to very high frequency resolution in the frequency-domain. We have presented the high frequency resolution terahertz time-domain spectroscopy of air and compared the results with the literature values. We have also fitted the complex susceptibility of air to the Lorentzian and Gaussian functions to extract the linewidths.

Long distance measurement with a femtosecond laser based frequency comb

NASA Astrophysics Data System (ADS)

Bhattacharya, N.; Cui, M.; Zeitouny, M. G.; Urbach, H. P.; van den Berg, S. A.

2017-11-01

Recent advances in the field of ultra-short pulse lasers have led to the development of reliable sources of carrier envelope phase stabilized femtosecond pulses. The pulse train generated by such a source has a frequency spectrum that consists of discrete, regularly spaced lines known as a frequency comb. In this case both the frequency repetition and the carrier-envelope-offset frequency are referenced to a frequency standard, like an atomic clock. As a result the accuracy of the frequency standard is transferred to the optical domain, with the frequency comb as transfer oscillator. These unique properties allow the frequency comb to be applied as a versatile tool, not only for time and frequency metrology, but also in fundamental physics, high-precision spectroscopy, and laser noise characterization. The pulse-to-pulse phase relationship of the light emitted by the frequency comb has opened up new directions for long range highly accurate distance measurement.

Poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles-catalyzed hydrolysis of ammonia borane for hydrogen generation

NASA Astrophysics Data System (ADS)

Rakap, Murat

2015-02-01

The catalytic use of highly efficient poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles (4.2 ± 1.9 nm) in the hydrolysis of ammonia-borane is reported. The catalyst is prepared by co-reduction of two metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and UV-Vis spectroscopy. They are recyclable and highly active for hydrogen generation from the hydrolysis of ammonia-borane even at very low concentrations and temperature, providing a record numbers of average turnover frequency value (125 mol H2/mol cat.min-1) and maximum hydrogen generation rate (3468 L H2 min-1 (mol cat)-1). They also provide activation energy of 51.7 ± 2 kJ/mol for the hydrolysis of ammonia borane.

Sum frequency generation (SFG) vibrational spectroscopy of planar phosphatidylethanolamine hybrid bilayer membranes under water.

PubMed

Kett, Peter J N; Casford, Michael T L; Davies, Paul B

2010-06-15

Sum frequency generation (SFG) spectroscopy has been used to study the structure of phosphatidylethanolamine hybrid bilayer membranes (HBMs) under water at ambient temperatures. The HBMs were formed using a modified Langmuir-Schaefer technique and consisted of a layer of dipalmitoyl phosphatidylethanolamine (DPPE) physisorbed onto an octadecanethiol (ODT) self-assembled monolayer (SAM) at a series of surface pressures from 1 to 40 mN m(-1). The DPPE and ODT were selectively deuterated so that the contributions to the SFG spectra from the two layers could be determined separately. SFG spectra in both the C-H and C-D stretching regions confirmed that a monolayer of DPPE had been adsorbed to the ODT SAM and that there were gauche defects within the alkyl chains of the phospholipid. On adsorption of a layer of DPPE, methylene modes from the ODT SAM were detected, indicating that the phospholipid had partially disordered the alkanethiol monolayer. SFG spectra recorded in air indicated that removal of water from the surface of the HBM resulted in disruption of the DPPE layer and the formation of phospholipid bilayers.

Substrate dependent structure of adsorbed aryl isocyanides studied by sum frequency generation (SFG) spectroscopy.

PubMed

Ito, Mikio; Noguchi, Hidenori; Ikeda, Katsuyoshi; Uosaki, Kohei

2010-04-07

Effects of metal substrate on the bonding nature of isocyanide group of two aryl isocyanides, 1,4-phenylene diisocyanide (PDI) and 4-methylphenyl isocyanide (MPI), and tilt angle of MPI were examined by measuring sum frequency generation (SFG) spectra of the self-assembled monolayers (SAMs) of these molecules on Au, Pt, Ag, and Pd surfaces. The SFG peaks due to "metal bonded" and "free"-NC groups were resolved by comparing the SFG spectra of PDI with IR spectra obtained by DFT calculations and previous results of vibrational spectroscopy. Based on the peak positions of the "metal bonded"-NC, it is clarified that while PDI and MPI were adsorbed at top sites on Au, Ag, and Pt surfaces, they adsorbed at bridge sites on the Pd surface. The tilt angles of MPI were determined from the intensity ratio between the SFG peaks of C-H symmetric and asymmetric stretching vibrational modes of the CH(3) group. The tilt angles of the MPI SAMs were in the order of Pt < Pd < Ag < Au, reflecting the bonding nature between the -NC group and the substrate atoms.

Environmental chemistry at vapor/water interfaces: insights from vibrational sum frequency generation spectroscopy.

PubMed

Jubb, Aaron M; Hua, Wei; Allen, Heather C

2012-01-01

The chemistry that occurs at surfaces has been an intense area of study for many years owing to its complexity and importance in describing a wide range of physical phenomena. The vapor/water interface is particularly interesting from an environmental chemistry perspective as this surface plays host to a wide range of chemistries that influence atmospheric and geochemical interactions. The application of vibrational sum frequency generation (VSFG), an inherently surface-specific, even-order nonlinear optical spectroscopy, enables the direct interrogation of various vapor/aqueous interfaces to elucidate the behavior and reaction of chemical species within the surface regime. In this review we discuss the application of VSFG to the study of a variety of atmospherically important systems at the vapor/aqueous interface. Chemical systems presented include inorganic ionic solutions prevalent in aqueous marine aerosols, small molecular solutes, and long-chain fatty acids relevant to fat-coated aerosols. The ability of VSFG to probe both the organization and reactions that may occur for these systems is highlighted. A future perspective toward the application of VSFG to the study of environmental interfaces is also provided.

Vibrational sum-frequency generation spectroscopy of ionic liquid 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate at the air-water interface

NASA Astrophysics Data System (ADS)

Saha, Ankur; SenGupta, Sumana; Kumar, Awadhesh; Choudhury, Sipra; Naik, Prakash D.

2016-08-01

The structure and orientation of room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate [PF3(C2F5)3], commonly known as [bmim][fap], have been investigated at the air-[bmim][fap] and air-water interfaces, employing vibrational sum-frequency generation (VSFG) spectroscopy. The VSFG spectra in the CH stretch region suggest presence of the [bmim] cation at the interfaces. Studies reveal that the butyl chain protrudes out into air, and the imidazolium ring lies almost planar to the interface. The CH stretch intensities get enhanced at the air-water interface, mainly because of polar orientation of imidazolium cation induced by interfacial water molecules. The OH stretch intensities are also enhanced at the air-water interface due to polar orientation of interfacial water molecules induced by [bmim][fap]. The Brewster angle microscopy suggests self aggregation of [bmim][fap] in the presence of water, and the aggregation becomes extensive showing dense surface domains with time. However, the surface pressure is almost unaffected due to aggregation.

Free-electron laser spectroscopy in biology, medicine, and materials science; Proceedings of the Meeting, Los Angeles, CA, Jan. 22, 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwettman, H.A.

1993-01-01

Various papers on FEL spectroscopy in biology, medicine, and materials science are presented. Individual topics addressed include: Vanderbilt University FEL Center, FIR FEL facility at the University of California/Santa Barbara, FEL research facilities and opportunities at Duke, facilities at the Stanford Picosecond FEL Center, FIR nonlinear response of electrons in semiconductor nanostructures, FIR harmonic generation from semiconductor heterostructures, intrinsic response times of double-barrier resonant tunneling diodes at tetrahertz frequencies, semiconductor spectroscopy and ablation processes with the Vanderbilt FEL. Also discussed are: picosecond nonlinear optics in semiconductor quantum wells with the SCA FEL, excitation spectroscopy of thin-film disordered semiconductors, biophysical applicationmore » of FELs, FEL investigation of energy transfer in condensed phase systems, probing protein photochemistry and dynamics with ultrafast infrared spectroscopy, plasma ablation of hard tissues by FEL, FEL irradiation of the cornea.« less

Capturing inhomogeneous broadening of the -CN stretch vibration in a Langmuir monolayer with high-resolution spectra and ultrafast vibrational dynamics in sum-frequency generation vibrational spectroscopy (SFG-VS)

NASA Astrophysics Data System (ADS)

Velarde, Luis; Wang, Hong-fei

2013-08-01

While in principle the frequency-domain and time-domain spectroscopic measurements should generate identical information for a given molecular system, the inhomogeneous character of surface vibrations in sum-frequency generation vibrational spectroscopy (SFG-VS) studies has only been studied with time-domain SFG-VS by mapping the decay of the vibrational polarization using ultrafast lasers, this due to the lack of SFG vibrational spectra with high enough spectral resolution and accurate enough lineshape. Here, with the recently developed high-resolution broadband SFG-VS (HR-BB-SFG-VS) technique, we show that the inhomogeneous lineshape can be obtained in the frequency-domain for the anchoring CN stretch of the 4-n-octyl-4'-cyanobiphenyl (8CB) Langmuir monolayer at the air-water interface, and that an excellent agreement with the time-domain SFG free-induction-decay can be established. We found that the 8CB CN stretch spectrum consists of a single peak centered at 2234.00 ± 0.01 cm-1 with a total linewidth of 10.9 ± 0.3 cm-1 at half maximum. The Lorentzian contribution accounts only for 4.7 ± 0.4 cm-1 to this width and the Gaussian (inhomogeneous) broadening for as much as 8.1 ± 0.2 cm-1. Polarization analysis of the -CN spectra showed that the -CN group is tilted 57° ± 2° from the surface normal. The large heterogeneity in the -CN spectrum is tentatively attributed to the -CN group interactions with the interfacial water molecules penetrated/accommodated into the 8CB monolayer, a unique phenomenon for the nCB Langmuir monolayers reported previously.

Capturing inhomogeneous broadening of the -CN stretch vibration in a Langmuir monolayer with high-resolution spectra and ultrafast vibrational dynamics in sum-frequency generation vibrational spectroscopy (SFG-VS).

PubMed

Velarde, Luis; Wang, Hong-fei

2013-08-28

While in principle the frequency-domain and time-domain spectroscopic measurements should generate identical information for a given molecular system, the inhomogeneous character of surface vibrations in sum-frequency generation vibrational spectroscopy (SFG-VS) studies has only been studied with time-domain SFG-VS by mapping the decay of the vibrational polarization using ultrafast lasers, this due to the lack of SFG vibrational spectra with high enough spectral resolution and accurate enough lineshape. Here, with the recently developed high-resolution broadband SFG-VS (HR-BB-SFG-VS) technique, we show that the inhomogeneous lineshape can be obtained in the frequency-domain for the anchoring CN stretch of the 4-n-octyl-4'-cyanobiphenyl (8CB) Langmuir monolayer at the air-water interface, and that an excellent agreement with the time-domain SFG free-induction-decay can be established. We found that the 8CB CN stretch spectrum consists of a single peak centered at 2234.00 ± 0.01 cm(-1) with a total linewidth of 10.9 ± 0.3 cm(-1) at half maximum. The Lorentzian contribution accounts only for 4.7 ± 0.4 cm(-1) to this width and the Gaussian (inhomogeneous) broadening for as much as 8.1 ± 0.2 cm(-1). Polarization analysis of the -CN spectra showed that the -CN group is tilted 57° ± 2° from the surface normal. The large heterogeneity in the -CN spectrum is tentatively attributed to the -CN group interactions with the interfacial water molecules penetrated/accommodated into the 8CB monolayer, a unique phenomenon for the nCB Langmuir monolayers reported previously.

Capturing inhomogeneous broadening of the -CN stretch vibration in a Langmuir monolayer with high-resolution spectra and ultrafast vibrational dynamics in sum-frequency generation vibrational spectroscopy (SFG-VS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Velarde Ruiz Esparza, Luis A.; Wang, Hongfei

2013-08-28

Even though in principle the frequency-domain and time-domain spectroscopic measurement should generate identical information for a given molecular system, inhomogeneous character of surface vibrations in the sum-frequency generation vibrational spectroscopy (SFG-VS) studies has only been studied with the time-domain SFGVS by mapping the decay of the vibrational polarization using ultrafast lasers, due to the lack of SFG vibrational spectra with high enough spectral resolution and accurate enough line shape. Here with recently developed high-resolution broadband SFG-VS (HR-BB-SFG-VS) we show that the inhomogeneous line shape can be obtained in the frequency-domain, for the anchoring CN stretch of the 4-n-octyl-4'-cyanobiphenyl (8CB) Langmuirmore » monolayer at the air-water interface, and that an excellent agreement with the time-domain SFG free-induction-decay (FID) results can be established. We found that the 8CB CN stretch spectrum consists of a single peak centered at 2234.00 + * 0.01 cm-1 with a total line width of 10.9 + - 0.3 cm-1 at half maximum. The Lorentzian contribution accounts only for 4:7 + -0:4 cm-1 to this width and the Gaussian (inhomogeneous) broadening for as much as 8:1+*0:2 cm-1. Polarization analysis of the -CN spectra showed that the -CN group is tilted 57 + - 2 degrees from the surface normal. The large heterogeneity in the -CN spectrum is tentatively attributed to the -CN group interactions with the interfacial water molecules penetrated/accomodated into the 8CB monolayer, a unique phenomenon for the nCB Langmuir monolayers reported previously.« less

Sphericity determination using resonant ultrasound spectroscopy

DOEpatents

Dixon, Raymond D.; Migliori, Albert; Visscher, William M.

1994-01-01

A method is provided for grading production quantities of spherical objects, such as roller balls for bearings. A resonant ultrasound spectrum (RUS) is generated for each spherical object and a set of degenerate sphere-resonance frequencies is identified. From the degenerate sphere-resonance frequencies and known relationships between degenerate sphere-resonance frequencies and Poisson's ratio, a Poisson's ratio can be determined, along with a "best" spherical diameter, to form spherical parameters for the sphere. From the RUS, fine-structure resonant frequency spectra are identified for each degenerate sphere-resonance frequency previously selected. From each fine-structure spectrum and associated sphere parameter values an asphericity value is determined. The asphericity value can then be compared with predetermined values to provide a measure for accepting or rejecting the sphere.

Sphericity determination using resonant ultrasound spectroscopy

DOEpatents

Dixon, R.D.; Migliori, A.; Visscher, W.M.

1994-10-18

A method is provided for grading production quantities of spherical objects, such as roller balls for bearings. A resonant ultrasound spectrum (RUS) is generated for each spherical object and a set of degenerate sphere-resonance frequencies is identified. From the degenerate sphere-resonance frequencies and known relationships between degenerate sphere-resonance frequencies and Poisson's ratio, a Poisson's ratio can be determined, along with a 'best' spherical diameter, to form spherical parameters for the sphere. From the RUS, fine-structure resonant frequency spectra are identified for each degenerate sphere-resonance frequency previously selected. From each fine-structure spectrum and associated sphere parameter values an asphericity value is determined. The asphericity value can then be compared with predetermined values to provide a measure for accepting or rejecting the sphere. 14 figs.

Progress Towards Chirped-Pulse Fourier Transform Thz Spectroscopy

NASA Astrophysics Data System (ADS)

Douglass, Kevin O.; Plusquellic, David F.; Gerecht, Eyal

2010-06-01

New opportunities are provided by the development of higher power THz frequency multiplier sources, the development of a broadband Chirped-Pulse FTMW spectroscopy technique at microwave and mm Wave frequencies, and recently demonstrated heterodyne hot electron bolometer detection technology in the THz frequency region with near quantum noise-limited performance and high spectral resolution. Combining these three technologies and extending the chirped-pulse technique to 0.85 THz enables a host of new applications. NIST is currently pursing applications as a point sensor for greenhouse gases, volatile organic compounds, and potentially human breath. The generation and detection of phase stable chirped pulses at 850 GHz will be demonstrated. A description of the experimental setup and preliminary data will be presented for nitrous oxide. G.G. Brown, B.C. Dian, K.O. Douglass, S.M. Geyer, S. Shipman and B.H. Pate, Rev.Sci.Instrum. 79 (2008) 053103. E. Gerecht, D. Gu, L. You, K.S. Yngvesson, IEEE TRANSACTIONS ON MICROWAVE THEORY AND TECHNIQUES. 56, (2008) 1083.

Broadband Rotational Spectroscopy

NASA Astrophysics Data System (ADS)

Pate, Brooks

2014-06-01

The past decade has seen several major technology advances in electronics operating at microwave frequencies making it possible to develop a new generation of spectrometers for molecular rotational spectroscopy. High-speed digital electronics, both arbitrary waveform generators and digitizers, continue on a Moore's Law-like development cycle that started around 1993 with device bandwidth doubling about every 36 months. These enabling technologies were the key to designing chirped-pulse Fourier transform microwave (CP-FTMW) spectrometers which offer significant sensitivity enhancements for broadband spectrum acquisition in molecular rotational spectroscopy. A special feature of the chirped-pulse spectrometer design is that it is easily implemented at low frequency (below 8 GHz) where Balle-Flygare type spectrometers with Fabry-Perot cavity designs become technologically challenging due to the mirror size requirements. The capabilities of CP-FTMW spectrometers for studies of molecular structure will be illustrated by the collaborative research effort we have been a part of to determine the structures of water clusters - a project which has identified clusters up to the pentadecamer. A second technology trend that impacts molecular rotational spectroscopy is the development of high power, solid state sources in the mm-wave/THz regions. Results from the field of mm-wave chirped-pulse Fourier transform spectroscopy will be described with an emphasis on new problems in chemical dynamics and analytical chemistry that these methods can tackle. The third (and potentially most important) technological trend is the reduction of microwave components to chip level using monolithic microwave integrated circuits (MMIC) - a technology driven by an enormous mass market in communications. Some recent advances in rotational spectrometer designs that incorporate low-cost components will be highlighted. The challenge to the high-resolution spectroscopy community - as posed by Frank De Lucia last year at the final meeting in Columbus - is what problems can we solve when real, fully capable spectrometers become essentially free to build?

Coherent ultra-violet to near-infrared generation in silica ridge waveguides

PubMed Central

Yoon Oh, Dong; Yang, Ki Youl; Fredrick, Connor; Ycas, Gabriel; Diddams, Scott A.; Vahala, Kerry J.

2017-01-01

Short duration, intense pulses of light can experience dramatic spectral broadening when propagating through lengths of optical fibre. This continuum generation process is caused by a combination of nonlinear optical effects including the formation of dispersive waves. Optical analogues of Cherenkov radiation, these waves allow a pulse to radiate power into a distant spectral region. In this work, efficient and coherent dispersive wave generation of visible to ultraviolet light is demonstrated in silica waveguides on a silicon chip. Unlike fibre broadeners, the arrays provide a wide range of emission wavelength choices on a single, compact chip. This new capability is used to simplify offset frequency measurements of a mode-locked frequency comb. The arrays can also enable mode-locked lasers to attain unprecedented tunable spectral reach for spectroscopy, bioimaging, tomography and metrology. PMID:28067233

High-density CMOS Microelectrode Array System for Impedance Spectroscopy and Imaging of Biological Cells.

PubMed

Vijay, Viswam; Raziyeh, Bounik; Amir, Shadmani; Jelena, Dragas; Alicia, Boos Julia; Axel, Birchler; Jan, Müller; Yihui, Chen; Andreas, Hierlemann

2017-01-26

A monolithic measurement platform was implemented to enable label-free in-vitro electrical impedance spectroscopy measurements of cells on multi-functional CMOS microelectrode array. The array includes 59,760 platinum microelectrodes, densely packed within a 4.5 mm × 2.5 mm sensing region at a pitch of 13.5 μm. The 32 on-chip lock-in amplifiers can be used to measure the impedance of any arbitrarily chosen electrodes on the array by applying a sinusoidal voltage, generated by an on-chip waveform generator with a frequency range from 1 Hz to 1 MHz, and measuring the respective current. Proof-of-concept measurements of impedance sensing and imaging are shown in this paper. Correlations between cell detection through optical microscopy and electrochemical impedance scanning were established.

Steering optical comb frequencies by rotating the polarization state

NASA Astrophysics Data System (ADS)

Zhang, Yanyan; Zhang, Xiaofei; Yan, Lulu; Zhang, Pan; Rao, Bingjie; Han, Wei; Guo, Wenge; Zhang, Shougang; Jiang, Haifeng

2017-12-01

Optical frequency combs, with precise control of repetition rate and carrier-envelope-offset frequency, have revolutionized many fields, such as fine optical spectroscopy, optical frequency standards, ultra-fast science research, ultra-stable microwave generation and precise ranging measurement. However, existing high bandwidth frequency control methods have small dynamic range, requiring complex hybrid control techniques. To overcome this limitation, we develop a new approach, where a home-made intra-cavity electro-optic modulator tunes polarization state of laser signal rather than only optical length of the cavity, to steer frequencies of a nonlinear-polarization-rotation mode-locked laser. By taking advantage of birefringence of the whole cavity, this approach results in not only broadband but also relative large-dynamic frequency control. Experimental results show that frequency control dynamic range increase at least one order in comparison with the traditional intra-cavity electro-optic modulator technique. In additional, this technique exhibits less side-effect than traditional frequency control methods.

Investigation of fingerprints for small polar molecules by using a tunable monochromatic THz source

NASA Astrophysics Data System (ADS)

Sun, Hongqian

Over the past 20 years, considerable efforts have been dedicated to the generation and the application of electromagnetic waves in the Terahertz (THz) regime. Among all of the proposed applications, the THz spectroscopy is probably the most mature and promising one. According to the previous reports, the THz spectroscopy has been extensively applied into many analysis fields, including the investigation of vibrational modes for the crystalline solids, the characterization of electron transport in the condense matters and the identification of explosive materials at a standoff distance. More interestingly, since most gas phase chemicals exhibit unique transition peaks in the THz spectra, one could in principle achieve highly accurate molecular fingerprinting and chemical sensing as well. However, all of the practical THz spectroscopy applications were still greatly hampered by the lack of suitable sources and detectors. In this thesis, a unique approach to measure the THz spectrum is developed based on a novel tunable narrowband source. Unlike the previous THz systems, high power THz pulses were generated by the difference frequency generation processes between two collinearly propagated near infrared laser beams. To tune the output THz signal frequency, one can simply adjust one of the incident beam frequencies. Therefore, based on a convenient wavelength tuning scheme, the transmission spectra can be measured for a series of polar gases with either similar or distinct molecular structures. According to the measured spectra, it is found that the obtained transition frequencies, absorption intensities and molecular constants are all in good agreement with the theoretical results tabulated in the molecular spectroscopic databases, such as the HITRAN database. By further analyzing the transition frequencies, it is also discovered that one can confidently identify each polar molecule and differentiate between various isotopic variants based on their characteristic molecular parameters (rotational constants). Compared to the commercially available FT-IR system, we have found that this technique has reached the same measurement accuracy. To quantitatively analyze the gas mixtures, we have measured the THz transmission spectra for two mixture samples (12CO/1 3CO, HBr/HCl) as well. Based on the Beer - Lambert Law, the partial pressure of the mixture constituent has been determined by comparing the transition peak absorption intensities. Considering the pressure broadening effect, further analysis on the detection limit of our tunable THz source is also provided. Compared to the previous techniques, this novel approach has demonstrated several advantages, including high accuracy, simplicity, robustness, larger dynamic range and longer lifetime. Therefore, it is believed that our tunable THz source has a great potential in the THz molecular spectroscopy and chemical sensing applications.

Spectroscopy of Magnetic Excitations in Magnetic Superconductors Using Vortex Motion

NASA Astrophysics Data System (ADS)

Bulaevskii, L. N.; Hruška, M.; Maley, M. P.

2005-11-01

In magnetic superconductors a moving vortex lattice is accompanied by an ac magnetic field which leads to the generation of spin waves. At resonance conditions the dynamics of vortices in magnetic superconductors changes drastically, resulting in strong peaks in the dc I-V characteristics at voltages at which the washboard frequency of the vortex lattice matches the spin wave frequency ωs(g), where g are the reciprocal vortex lattice vectors. We show that if the washboard frequency lies above the magnetic gap, measurement of the I-V characteristics provides a new method to obtain information on the spectrum of magnetic excitations in borocarbides and cuprate layered magnetic superconductors.

Laser spectroscopy of a halocarbocation in the gas phase: CH2I+.

PubMed

Tao, Chong; Mukarakate, Calvin; Reid, Scott A

2006-07-26

We report the first gas-phase observation of the electronic spectrum of a simple halocarbocation, CH2I+. The ion was generated rotationally cold (Trot approximately 20 K) using pulsed discharge methods and was detected via laser spectroscopy. The identity of the spectral carrier was confirmed by modeling the rotational contour observed in the excitation spectra and by comparison of ground state vibrational frequencies determined by single vibronic level emission spectroscopy with Density Functional Theory (DFT) predictions. The transition was assigned as 3A1 <-- X1A1. This initial detection of the electronic spectrum of a halocarbocation in the gas phase should open new avenues for study of the structure and reactivity of these important ions.

Far off-resonance laser frequency stabilization using multipass cells in Faraday rotation spectroscopy.

PubMed

Quan, Wei; Li, Yang; Li, Rujie; Shang, Huining; Fang, Zishan; Qin, Jie; Wan, Shuangai

2016-04-01

We propose a far off-resonance laser frequency stabilization method by using multipass cells in Rb Faraday rotation spectroscopy. Based on the detuning equation, if multipass cells with several meters optical path length are used in the conventional Faraday spectroscopy, the detuning of the lock point can be extended much further from the alkali metal resonance. A plate beam splitter was used to generate two different Faraday signals at the same time. The transmitted optical path length was L=50  mm and the reflected optical path length was 2L=100  mm. When the optical path length doubled, the detuning of the lock points moved further away from the atomic resonance. The temperature dependence of the detuning of the lock point was also analyzed. A temperature-insensitive lock point was found near resonance when the cell temperature was between 110°C and 130°C. We achieved an rms fluctuation of 0.9 MHz/23 h at a detuning of 0.5 GHz. A frequency drift of 16 MHz/h at a detuning of -5.6  GHz and 4 MHz/h at a detuning of -5.2  GHz were also obtained for the transmitted and reflected light Faraday signal.

Fiber-laser frequency combs for the generation of tunable single-frequency laser lines, mm- and THz-waves and sinc-shaped Nyquist pulses

NASA Astrophysics Data System (ADS)

Schneider, Thomas

2015-03-01

High-quality frequency comb sources like femtosecond-lasers have revolutionized the metrology of fundamental physical constants. The generated comb consists of frequency lines with an equidistant separation over a bandwidth of several THz. This bandwidth can be broadened further to a super-continuum of more than an octave through propagation in nonlinear media. The frequency separation between the lines is defined by the repetition rate and the width of each comb line can be below 1 Hz, even without external stabilization. By extracting just one of these lines, an ultra-narrow linewidth, tunable laser line for applications in communications and spectroscopy can be generated. If two lines are extracted, the superposition of these lines in an appropriate photo-mixer produces high-quality millimeter- and THz-waves. The extraction of several lines can be used for the creation of almost-ideally sinc-shaped Nyquist pulses, which enable optical communications with the maximum-possible baud rate. Especially combs generated by low-cost, small-footprint fs-fiber lasers are very promising. However due to the resonator length, the comb frequencies have a typical separation of 80 - 100 MHz, far too narrow for the selection of single tones with standard optical filters. Here the extraction of single lines of an fs-fiber laser by polarization pulling assisted stimulated Brillouin scattering is presented. The application of these extracted lines as ultra-narrow, stable and tunable laser lines, for the generation of very high-quality mm and THz-waves with an ultra-narrow linewidth and phase noise and for the generation of sinc-shaped Nyquist pulses with arbitrary bandwidth and repetition rate is discussed.

Wetting effect on optical sum frequency generation (SFG) spectra of D-glucose, D-fructose, and sucrose

NASA Astrophysics Data System (ADS)

Hieu, Hoang Chi; Li, Hongyan; Miyauchi, Yoshihiro; Mizutani, Goro; Fujita, Naoko; Nakamura, Yasunori

2015-03-01

We report a sum frequency generation (SFG) spectroscopy study of D-glucose, D-fructose and sucrose in the Csbnd H stretching vibration regime. Wetting effect on the SFG spectra was investigated. The SFG spectrum of D-glucose changed from that of α-D-glucose into those of α-D-glucose monohydrate by wetting. The SFG spectra showed evidence of a small change of β-D-fructopyranose into other anomers by wetting. SFG spectra of sucrose did not change by wetting. Assignments of the vibrational peaks in the SFG spectra of the three sugars in the dry and wet states were performed in the Csbnd H stretching vibration region near 3000 cm-1.

Wetting effect on optical sum frequency generation (SFG) spectra of d-glucose, d-fructose, and sucrose.

PubMed

Hieu, Hoang Chi; Li, Hongyan; Miyauchi, Yoshihiro; Mizutani, Goro; Fujita, Naoko; Nakamura, Yasunori

2015-03-05

We report a sum frequency generation (SFG) spectroscopy study of d-glucose, d-fructose and sucrose in the CH stretching vibration regime. Wetting effect on the SFG spectra was investigated. The SFG spectrum of d-glucose changed from that of α-d-glucose into those of α-d-glucose monohydrate by wetting. The SFG spectra showed evidence of a small change of β-d-fructopyranose into other anomers by wetting. SFG spectra of sucrose did not change by wetting. Assignments of the vibrational peaks in the SFG spectra of the three sugars in the dry and wet states were performed in the CH stretching vibration region near 3000cm(-1). Copyright © 2014 Elsevier B.V. All rights reserved.

OH Production Enhancement in Bubbling Pulsed Discharges

NASA Astrophysics Data System (ADS)

Lungu, Cristian P.; Porosnicu, Corneliu; Jepu, Ionut; Chiru, Petrica; Zaroschi, Valentin; Lungu, Ana M.; Saito, Nagahiro; Bratescu, Maria; Takai, Osamu; Velea, Theodor; Predica, Vasile

2010-10-01

The generation of active species, such as H2O2, O*, OH*, HO2*, O3, N2*, etc, produced in aqueous solutions by HV pulsed discharges was studied in order to find the most efficient way in waste water treatment taking into account that these species are almost stronger oxidizers than ozone. Plasma was generated inside gas bubbles formed by the argon, air and oxygen gas flow between the special designed electrodes. The pulse width and pulse frequency influence was studied in order to increase the efficiency of the OH active species formation. The produced active species were investigated by optical emission spectroscopy and correlated with electrical parameters of the discharges (frequency, pulse width, amplitude, and rise and decay time).

Discharge Characteristics of DC Arc Water Plasma for Environmental Applications

NASA Astrophysics Data System (ADS)

Li, Tianming; Sooseok, Choi; Takayuki, Watanabe

2012-12-01

A water plasma was generated by DC arc discharge with a hafnium embedded rod-type cathode and a nozzle-type anode. The discharge characteristics were examined by changing the operation parameter of the arc current. The dynamic behavior of the arc discharge led to significant fluctuations in the arc voltage and its frequency. Analyses of the high speed image and the arc voltage waveform showed that the arc discharge was in the restrike mode and its frequency varied within several tens of kilohertz according to the operating conditions. The larger thermal plasma volume was generated by the higher flow from the forming steam with a higher restrike frequency in the higher arc current conditions. In addition, the characteristics of the water plasma jet were investigated by means of optical emission spectroscopy to identify the abundant radicals required in an efficient waste treatment process.

An octave-spanning mid-infrared frequency comb generated in a silicon nanophotonic wire waveguide

PubMed Central

Kuyken, Bart; Ideguchi, Takuro; Holzner, Simon; Yan, Ming; Hänsch, Theodor W.; Van Campenhout, Joris; Verheyen, Peter; Coen, Stéphane; Leo, Francois; Baets, Roel; Roelkens, Gunther; Picqué, Nathalie

2015-01-01

Laser frequency combs, sources with a spectrum consisting of hundred thousands evenly spaced narrow lines, have an exhilarating potential for new approaches to molecular spectroscopy and sensing in the mid-infrared region. The generation of such broadband coherent sources is presently under active exploration. Technical challenges have slowed down such developments. Identifying a versatile highly nonlinear medium for significantly broadening a mid-infrared comb spectrum remains challenging. Here we take a different approach to spectral broadening of mid-infrared frequency combs and investigate CMOS-compatible highly nonlinear dispersion-engineered silicon nanophotonic waveguides on a silicon-on-insulator chip. We record octave-spanning (1,500–3,300 nm) spectra with a coupled input pulse energy as low as 16 pJ. We demonstrate phase-coherent comb spectra broadened on a room-temperature-operating CMOS-compatible chip. PMID:25697764

Spectral linewidth of spin-current nano-oscillators driven by nonlocal spin injection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Demidov, V. E., E-mail: demidov@uni-muenster.de; Divinskiy, B.; Urazhdin, S.

2015-11-16

We study experimentally the auto-oscillation characteristics of magnetic nano-oscillators driven by pure spin currents generated by nonlocal spin injection. By combining micro-focus Brillouin light scattering spectroscopy with electronic microwave spectroscopy, we are able to simultaneously perform both the spatial and the high-resolution spectral analyses of auto-oscillations induced by spin current. We find that the devices exhibit a highly coherent dynamics with the spectral linewidth of a few megahertz at room temperature. This narrow linewidth can be achieved over a wide range of operational frequencies, demonstrating a significant potential of nonlocal oscillators for applications.

Detection of elemental mercury by multimode diode laser correlation spectroscopy.

PubMed

Lou, Xiutao; Somesfalean, Gabriel; Svanberg, Sune; Zhang, Zhiguo; Wu, Shaohua

2012-02-27

We demonstrate a method for elemental mercury detection based on correlation spectroscopy employing UV laser radiation generated by sum-frequency mixing of two visible multimode diode lasers. Resonance matching of the multimode UV laser is achieved in a wide wavelength range and with good tolerance for various operating conditions. Large mode-hops provide an off-resonance baseline, eliminating interferences from other gas species with broadband absorption. A sensitivity of 1 μg/m3 is obtained for a 1-m path length and 30-s integration time. The performance of the system shows promise for mercury monitoring in industrial applications.

Observation and theory of reorientation-induced spectral diffusion in polarization-selective 2D IR spectroscopy.

PubMed

Kramer, Patrick L; Nishida, Jun; Giammanco, Chiara H; Tamimi, Amr; Fayer, Michael D

2015-05-14

In nearly all applications of ultrafast multidimensional infrared spectroscopy, the spectral degrees of freedom (e.g., transition frequency) and the orientation of the transition dipole are assumed to be decoupled. We present experimental results which confirm that frequency fluctuations can be caused by rotational motion and observed under appropriate conditions. A theory of the frequency-frequency correlation function (FFCF) observable under various polarization conditions is introduced, and model calculations are found to reproduce the qualitative trends in FFCF rates. The FFCF determined with polarization-selective two-dimensional infrared (2D IR) spectroscopy is a direct reporter of the frequency-rotational coupling. For the solute methanol in a room temperature ionic liquid, the FFCF of the hydroxyl (O-D) stretch decays due to spectral diffusion with different rates depending on the polarization of the excitation pulses. The 2D IR vibrational echo pulse sequence consists of three excitation pulses that generate the vibrational echo, a fourth pulse. A faster FFCF decay is observed when the first two excitation pulses are polarized perpendicular to the third pulse and the echo, 〈XXY Y〉, than in the standard all parallel configuration, 〈XXXX〉, in which all four pulses have the same polarization. The 2D IR experiment with polarizations 〈XY XY〉 ("polarization grating" configuration) gives a FFCF that decays even more slowly than in the 〈XXXX〉 configuration. Polarization-selective 2D IR spectra of bulk water do not exhibit polarization-dependent FFCF decays; spectral diffusion is effectively decoupled from reorientation in the water system.

Observation and theory of reorientation-induced spectral diffusion in polarization-selective 2D IR spectroscopy

NASA Astrophysics Data System (ADS)

Kramer, Patrick L.; Nishida, Jun; Giammanco, Chiara H.; Tamimi, Amr; Fayer, Michael D.

2015-05-01

In nearly all applications of ultrafast multidimensional infrared spectroscopy, the spectral degrees of freedom (e.g., transition frequency) and the orientation of the transition dipole are assumed to be decoupled. We present experimental results which confirm that frequency fluctuations can be caused by rotational motion and observed under appropriate conditions. A theory of the frequency-frequency correlation function (FFCF) observable under various polarization conditions is introduced, and model calculations are found to reproduce the qualitative trends in FFCF rates. The FFCF determined with polarization-selective two-dimensional infrared (2D IR) spectroscopy is a direct reporter of the frequency-rotational coupling. For the solute methanol in a room temperature ionic liquid, the FFCF of the hydroxyl (O-D) stretch decays due to spectral diffusion with different rates depending on the polarization of the excitation pulses. The 2D IR vibrational echo pulse sequence consists of three excitation pulses that generate the vibrational echo, a fourth pulse. A faster FFCF decay is observed when the first two excitation pulses are polarized perpendicular to the third pulse and the echo, , than in the standard all parallel configuration, , in which all four pulses have the same polarization. The 2D IR experiment with polarizations ("polarization grating" configuration) gives a FFCF that decays even more slowly than in the configuration. Polarization-selective 2D IR spectra of bulk water do not exhibit polarization-dependent FFCF decays; spectral diffusion is effectively decoupled from reorientation in the water system.

Characterizing Far-infrared Laser Emissions and the Measurement of Their Frequencies.

PubMed

Jackson, Michael; Zink, Lyndon R

2015-12-18

The generation and subsequent measurement of far-infrared radiation has found numerous applications in high-resolution spectroscopy, radio astronomy, and Terahertz imaging. For about 45 years, the generation of coherent, far-infrared radiation has been accomplished using the optically pumped molecular laser. Once far-infrared laser radiation is detected, the frequencies of these laser emissions are measured using a three-laser heterodyne technique. With this technique, the unknown frequency from the optically pumped molecular laser is mixed with the difference frequency between two stabilized, infrared reference frequencies. These reference frequencies are generated by independent carbon dioxide lasers, each stabilized using the fluorescence signal from an external, low pressure reference cell. The resulting beat between the known and unknown laser frequencies is monitored by a metal-insulator-metal point contact diode detector whose output is observed on a spectrum analyzer. The beat frequency between these laser emissions is subsequently measured and combined with the known reference frequencies to extrapolate the unknown far-infrared laser frequency. The resulting one-sigma fractional uncertainty for laser frequencies measured with this technique is ± 5 parts in 10(7). Accurately determining the frequency of far-infrared laser emissions is critical as they are often used as a reference for other measurements, as in the high-resolution spectroscopic investigations of free radicals using laser magnetic resonance. As part of this investigation, difluoromethane, CH2F2, was used as the far-infrared laser medium. In all, eight far-infrared laser frequencies were measured for the first time with frequencies ranging from 0.359 to 1.273 THz. Three of these laser emissions were discovered during this investigation and are reported with their optimal operating pressure, polarization with respect to the CO2 pump laser, and strength.

Characterizing Far-infrared Laser Emissions and the Measurement of Their Frequencies

PubMed Central

Jackson, Michael; Zink, Lyndon R.

2015-01-01

The generation and subsequent measurement of far-infrared radiation has found numerous applications in high-resolution spectroscopy, radio astronomy, and Terahertz imaging. For about 45 years, the generation of coherent, far-infrared radiation has been accomplished using the optically pumped molecular laser. Once far-infrared laser radiation is detected, the frequencies of these laser emissions are measured using a three-laser heterodyne technique. With this technique, the unknown frequency from the optically pumped molecular laser is mixed with the difference frequency between two stabilized, infrared reference frequencies. These reference frequencies are generated by independent carbon dioxide lasers, each stabilized using the fluorescence signal from an external, low pressure reference cell. The resulting beat between the known and unknown laser frequencies is monitored by a metal-insulator-metal point contact diode detector whose output is observed on a spectrum analyzer. The beat frequency between these laser emissions is subsequently measured and combined with the known reference frequencies to extrapolate the unknown far-infrared laser frequency. The resulting one-sigma fractional uncertainty for laser frequencies measured with this technique is ± 5 parts in 107. Accurately determining the frequency of far-infrared laser emissions is critical as they are often used as a reference for other measurements, as in the high-resolution spectroscopic investigations of free radicals using laser magnetic resonance. As part of this investigation, difluoromethane, CH2F2, was used as the far-infrared laser medium. In all, eight far-infrared laser frequencies were measured for the first time with frequencies ranging from 0.359 to 1.273 THz. Three of these laser emissions were discovered during this investigation and are reported with their optimal operating pressure, polarization with respect to the CO2 pump laser, and strength. PMID:26709957

Spectral purity and tunability of terahertz quantum cascade laser sources based on intracavity difference-frequency generation.

PubMed

Consolino, Luigi; Jung, Seungyong; Campa, Annamaria; De Regis, Michele; Pal, Shovon; Kim, Jae Hyun; Fujita, Kazuue; Ito, Akio; Hitaka, Masahiro; Bartalini, Saverio; De Natale, Paolo; Belkin, Mikhail A; Vitiello, Miriam Serena

2017-09-01

Terahertz sources based on intracavity difference-frequency generation in mid-infrared quantum cascade lasers (THz DFG-QCLs) have recently emerged as the first monolithic electrically pumped semiconductor sources capable of operating at room temperature across the 1- to 6-THz range. Despite tremendous progress in power output, which now exceeds 1 mW in pulsed and 10 μW in continuous-wave regimes at room temperature, knowledge of the major figure of merits of these devices for high-precision spectroscopy, such as spectral purity and absolute frequency tunability, is still lacking. By exploiting a metrological grade system comprising a terahertz frequency comb synthesizer, we measure, for the first time, the free-running emission linewidth (LW), the tuning characteristics, and the absolute center frequency of individual emission lines of these sources with an uncertainty of 4 × 10 -10 . The unveiled emission LW (400 kHz at 1-ms integration time) indicates that DFG-QCLs are well suited to operate as local oscillators and to be used for a variety of metrological, spectroscopic, communication, and imaging applications that require narrow-LW THz sources.

Remotely manageable system for stabilizing femtosecond lasers

NASA Astrophysics Data System (ADS)

Cizek, Martin; Hucl, Vaclav; Smid, Radek; Mikel, Bretislav; Lazar, Josef; Cip, Ondrej

2014-05-01

In the field of precise measurement of optical frequencies, laser spectroscopy and interferometric distance surveying the optical frequency synthesizers (femtosecond combs) are used as optical frequency references. They generate thousands of narrow-linewidth coherent optical frequencies at the same time. The spacing of generated components equals to the repetition frequency of femtosecond pulses of the laser. The position of the comb spectrum has a frequency offset that is derived from carrier to envelope frequency difference. The repetition frequency and mentioned frequency offset belong to main controlled parameters of the optical frequency comb. If these frequencies are electronically locked an ultrastable frequency standard (i.e. H-maser, Cs- or Rb- clock), its relative stability is transferred to the optical frequency domain. We present a complete digitally controlled signal processing chain for phase-locked loop (PLL) control of the offset frequency. The setup is able to overcome some dropouts caused by the femtosecond laser non-stabilities (temperature drifts, ripple noise and electricity spikes). It is designed as a two-stage control loop, where controlled offset frequency is permanently monitored by digital signal processing. In case of dropouts of PLL, the frequency-locked loop keeps the controlled frequency in the required limits. The presented work gives the possibility of long-time operation of femtosecond combs which is necessary when the optical frequency stability measurement of ultra-stable lasers is required. The detailed description of the modern solution of the PLL with remote management is presented.

Comb-Resolved Dual-Comb Spectroscopy Stabilized by Free-Running Continuous-Wave Lasers

NASA Astrophysics Data System (ADS)

Kuse, Naoya; Ozawa, Akira; Kobayashi, Yohei

2012-11-01

We demonstrate dual-comb spectroscopy with relatively phase-locked two frequency combs, instead of frequency combs firmly fixed to the absolute frequency references. By stabilizing two beat frequencies between two mode-locked lasers at different wavelengths observed via free-running continuous-wave (CW) lasers, two combs are tightly phase locked to each other. The frequency noise of the CW lasers barely affects the performance of dual-comb spectroscopy because of the extremely fast common-mode noise rejection. Transform-limited comb-resolved dual-comb spectroscopy with a 6 Hz radio frequency linewidth is demonstrated by the use of Yb-fiber oscillators.

Heterodyne mixing of millimetre electromagnetic waves and sub-THz sound in a semiconductor device

PubMed Central

Heywood, Sarah L.; Glavin, Boris A.; Beardsley, Ryan P.; Akimov, Andrey V.; Carr, Michael W.; Norman, James; Norton, Philip C.; Prime, Brian; Priestley, Nigel; Kent, Anthony J.

2016-01-01

We demonstrate heterodyne mixing of a 94 GHz millimetre wave photonic signal, supplied by a Gunn diode oscillator, with coherent acoustic waves of frequency ~100 GHz, generated by pulsed laser excitation of a semiconductor surface. The mixing takes place in a millimetre wave Schottky diode, and the intermediate frequency electrical signal is in the 1–12 GHz range. The mixing process preserves all the spectral content in the acoustic signal that falls within the intermediate frequency bandwidth. Therefore this technique may find application in high-frequency acoustic spectroscopy measurements, exploiting the nanometre wavelength of sub-THz sound. The result also points the way to exploiting acoustoelectric effects in photonic devices working at sub-THz and THz frequencies, which could provide functionalities at these frequencies, e.g. acoustic wave filtering, that are currently in widespread use at lower (GHz) frequencies. PMID:27477841

Photon entanglement signatures in difference-frequency-generation

PubMed Central

Roslyak, Oleksiy; Mukamel, Shaul

2010-01-01

In response to quantum optical fields, pairs of molecules generate coherent nonlinear spectroscopy signals. Homodyne signals are given by sums over terms each being a product of Liouville space pathways of the pair of molecules times the corresponding optical field correlation function. For classical fields all field correlation functions may be factorized and become identical products of field amplitudes. The signal is then given by the absolute square of a susceptibility which in turn is a sum over pathways of a single molecule. The molecular pathways of different molecules in the pair are uncorrelated in this case (each path of a given molecule can be accompanied by any path of the other). However, entangled photons create an entanglement between the molecular pathways. We use the superoperator nonequlibrium Green’s functions formalism to demonstrate the signatures of this pathway-entanglement in the difference frequency generation signal. Comparison is made with an analogous incoherent two-photon fluorescence signal. PMID:19158927

Broadband sum-frequency generation using d₃₃ in periodically poled LiNbO₃ thin film in the telecommunications band.

PubMed

Li, Guangzhen; Chen, Yuping; Jiang, Haowei; Chen, Xianfeng

2017-03-01

We demonstrate the first, to the best of our knowledge, type-0 broadband sum-frequency generation (SFG) based on single-crystal periodically poled LiNbO₃ (PPLN) thin film. The broad bandwidth property was largely tuned from mid-infrared region to the telecommunications band by engineering the thickness of PPLN from bulk crystal to nanoscale. It provides SFG a solution with both broadband and high efficiency by using the highest nonlinear coefficient d₃₃ instead of d₃₁ in type-I broadband SFG or second-harmonic generation. The measured 3 dB upconversion bandwidth is about 15.5 nm for a 4 cm long single crystal at 1530 nm wavelength. It can find applications in chip-scale spectroscopy, quantum information processing, LiNbO₃-thin-film-based microresonator and optical nonreciprocity devices, etc.

Dual frequency comb metrology with one fiber laser

NASA Astrophysics Data System (ADS)

Zhao, Xin; Takeshi, Yasui; Zheng, Zheng

2016-11-01

Optical metrology techniques based on dual optical frequency combs have emerged as a hotly studied area targeting a wide range of applications from optical spectroscopy to microwave and terahertz frequency measurement. Generating two sets of high-quality comb lines with slightly different comb-tooth spacings with high mutual coherence and stability is the key to most of the dual-comb schemes. The complexity and costs of such laser sources and the associated control systems to lock the two frequency combs hinder the wider adoption of such techniques. Here we demonstrate a very simple and rather different approach to tackle such a challenge. By employing novel laser cavity designs in a mode-locked fiber laser, a simple fiber laser setup could emit dual-comb pulse output with high stability and good coherence between the pulse trains. Based on such lasers, comb-tooth-resolved dual-comb optical spectroscopy is demonstrated. Picometer spectral resolving capability could be realized with a fiber-optic setup and a low-cost data acquisition system and standard algorithms. Besides, the frequency of microwave signals over a large range can be determined based on a simple setup. Our results show the capability of such single-fiber-laser-based dual-comb scheme to reduce the complexity and cost of dual-comb systems with excellent quality for different dual-comb applications.

Elucidation of Compression-Induced Surface Crystallization in Amorphous Tablets Using Sum Frequency Generation (SFG) Microscopy.

PubMed

Mah, Pei T; Novakovic, Dunja; Saarinen, Jukka; Van Landeghem, Stijn; Peltonen, Leena; Laaksonen, Timo; Isomäki, Antti; Strachan, Clare J

2017-05-01

To investigate the effect of compression on the crystallization behavior in amorphous tablets using sum frequency generation (SFG) microscopy imaging and more established analytical methods. Tablets containing neat amorphous griseofulvin with/without excipients (silica, hydroxypropyl methylcellulose acetate succinate (HPMCAS), microcrystalline cellulose (MCC) and polyethylene glycol (PEG)) were prepared. They were analyzed upon preparation and storage using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy (SEM) and SFG microscopy. Compression-induced crystallization occurred predominantly on the surface of the neat amorphous griseofulvin tablets, with minimal crystallinity being detected in the core of the tablets. The presence of various types of excipients was not able to mitigate the compression-induced surface crystallization of the amorphous griseofulvin tablets. However, the excipients affected the crystallization rate of amorphous griseofulvin in the core of the tablet upon compression and storage. SFG microscopy can be used in combination with ATR-FTIR spectroscopy and SEM to understand the crystallization behaviour of amorphous tablets upon compression and storage. When selecting excipients for amorphous formulations, it is important to consider the effect of the excipients on the physical stability of the amorphous formulations.

Investigating buried polymer interfaces using sum frequency generation vibrational spectroscopy

PubMed Central

Chen, Zhan

2010-01-01

This paper reviews recent progress in the studies of buried polymer interfaces using sum frequency generation (SFG) vibrational spectroscopy. Both buried solid/liquid and solid/solid interfaces involving polymeric materials are discussed. SFG studies of polymer/water interfaces show that different polymers exhibit varied surface restructuring behavior in water, indicating the importance of probing polymer/water interfaces in situ. SFG has also been applied to the investigation of interfaces between polymers and other liquids. It has been found that molecular interactions at such polymer/liquid interfaces dictate interfacial polymer structures. The molecular structures of silane molecules, which are widely used as adhesion promoters, have been investigated using SFG at buried polymer/silane and polymer/polymer interfaces, providing molecular-level understanding of polymer adhesion promotion. The molecular structures of polymer/solid interfaces have been examined using SFG with several different experimental geometries. These results have provided molecular-level information about polymer friction, adhesion, interfacial chemical reactions, interfacial electronic properties, and the structure of layer-by-layer deposited polymers. Such research has demonstrated that SFG is a powerful tool to probe buried interfaces involving polymeric materials, which are difficult to study by conventional surface sensitive analytical techniques. PMID:21113334

Theoretical vibrational sum-frequency generation spectroscopy of water near lipid and surfactant monolayer interfaces. II. Two-dimensional spectra.

PubMed

Roy, S; Gruenbaum, S M; Skinner, J L

2014-12-14

The structural stability and function of biomolecules is strongly influenced by the dynamics and hydrogen bonding of interfacial water. Understanding and characterizing the dynamics of these water molecules require a surface-sensitive technique such as two-dimensional vibrational sum-frequency generation (2DSFG) spectroscopy. We have combined theoretical 2DSFG calculations with molecular dynamics simulations in order to investigate the dynamics of water near different lipid and surfactant monolayer surfaces. We show that 2DSFG can distinguish the dynamics of interfacial water as a function of the lipid charge and headgroup chemistry. The dynamics of water is slow compared to the bulk near water-zwitterionic and water-anionic interfaces due to conformational constraints on interfacial water imposed by strong phosphate-water hydrogen bonding. The dynamics of water is somewhat faster near water-cationic lipid interfaces as no such constraint is present. Using hydrogen bonding and rotational correlation functions, we characterize the dynamics of water as a function of the distance from the interface between water and zwitterionic lipids. We find that there is a transition from bulk-like to interface-like dynamics approximately 7 Å away from a zwitterionic phosphatidylcholine monolayer surface.

Time-Domain Nuclear Magnetic Resonance (TD-NMR) and Chemometrics for Determination of Fat Content in Commercial Products of Milk Powder.

PubMed

Nascimento, Paloma Andrade Martins; Barsanelli, Paulo Lopes; Rebellato, Ana Paula; Pallone, Juliana Azevedo Lima; Colnago, Luiz Alberto; Pereira, Fabíola Manhas Verbi

2017-03-01

This study shows the use of time-domain (TD)-NMR transverse relaxation (T2) data and chemometrics in the nondestructive determination of fat content for powdered food samples such as commercial dried milk products. Most proposed NMR spectroscopy methods for measuring fat content correlate free induction decay or echo intensities with the sample's mass. The need for the sample's mass limits the analytical frequency of NMR determination, because weighing the samples is an additional step in this procedure. Therefore, the method proposed here is based on a multivariate model of T2 decay, measured with Carr-Purcell-Meiboom-Gill pulse sequence and reference values of fat content. The TD-NMR spectroscopy method shows high correlation (r = 0.95) with the lipid content, determined by the standard extraction method of Bligh and Dyer. For comparison, fat content determination was also performed using a multivariate model with near-IR (NIR) spectroscopy, which is also a nondestructive method. The advantages of the proposed TD-NMR method are that it (1) minimizes toxic residue generation, (2) performs measurements with high analytical frequency (a few seconds per analysis), and (3) does not require sample preparation (such as pelleting, needed for NIR spectroscopy analyses) or weighing the samples.

Half-Watt average power femtosecond source spanning 3-8 µm based on subharmonic generation in GaAs

NASA Astrophysics Data System (ADS)

Smolski, Viktor; Vasilyev, Sergey; Moskalev, Igor; Mirov, Mike; Ru, Qitian; Muraviev, Andrey; Schunemann, Peter; Mirov, Sergey; Gapontsev, Valentin; Vodopyanov, Konstantin

2018-06-01

Frequency combs with a wide instantaneous spectral span covering the 3-20 µm molecular fingerprint region are highly desirable for broadband and high-resolution frequency comb spectroscopy, trace molecular detection, and remote sensing. We demonstrate a novel approach for generating high-average-power middle-infrared (MIR) output suitable for producing frequency combs with an instantaneous spectral coverage close to 1.5 octaves. Our method is based on utilizing a highly-efficient and compact Kerr-lens mode-locked Cr2+:ZnS laser operating at 2.35-µm central wavelength with 6-W average power, 77-fs pulse duration, and high 0.9-GHz repetition rate; to pump a degenerate (subharmonic) optical parametric oscillator (OPO) based on a quasi-phase-matched GaAs crystal. Such subharmonic OPO is a nearly ideal frequency converter capable of extending the benefits of frequency combs based on well-established mode-locked pump lasers to the MIR region through rigorous, phase- and frequency-locked down conversion. We report a 0.5-W output in the form of an ultra-broadband spectrum spanning 3-8 µm measured at 50-dB level.

Flexible approach to vibrational sum-frequency generation using shaped near-infrared light

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chowdhury, Azhad U.; Liu, Fangjie; Watson, Brianna R.

We describe a new approach that expands the utility of vibrational sum-frequency generation (vSFG) spectroscopy using shaped near-infrared (NIR) laser pulses. Here, we demonstrate that arbitrary pulse shapes can be specified to match experimental requirements without the need for changes to the optical alignment. In this way, narrowband NIR pulses as long as 5.75 ps are readily generated, with a spectral resolution of about 2.5 cm -1, an improvement of approximately a factor of 3 compared to a typical vSFG system. Moreover, the utility of having complete control over the NIR pulse characteristics is demonstrated through nonresonant background suppression frommore » a metallic substrate by generating an etalon waveform in the pulse shaper. The flexibility afforded by switching between arbitrary NIR waveforms at the sample position with the same instrument geometry expands the type of samples that can be studied without extensive modifications to existing apparatuses or large investments in specialty optics.« less

Flexible approach to vibrational sum-frequency generation using shaped near-infrared light

DOE PAGES

Chowdhury, Azhad U.; Liu, Fangjie; Watson, Brianna R.; ...

2018-04-23

We describe a new approach that expands the utility of vibrational sum-frequency generation (vSFG) spectroscopy using shaped near-infrared (NIR) laser pulses. Here, we demonstrate that arbitrary pulse shapes can be specified to match experimental requirements without the need for changes to the optical alignment. In this way, narrowband NIR pulses as long as 5.75 ps are readily generated, with a spectral resolution of about 2.5 cm -1, an improvement of approximately a factor of 3 compared to a typical vSFG system. Moreover, the utility of having complete control over the NIR pulse characteristics is demonstrated through nonresonant background suppression frommore » a metallic substrate by generating an etalon waveform in the pulse shaper. The flexibility afforded by switching between arbitrary NIR waveforms at the sample position with the same instrument geometry expands the type of samples that can be studied without extensive modifications to existing apparatuses or large investments in specialty optics.« less

Laser Materials and Laser Spectroscopy - A Satellite Meeting of IQEC '88

NASA Astrophysics Data System (ADS)

Wang, Zhijiang; Zhang, Zhiming

1989-03-01

The Table of Contents for the book is as follows: * Laser Materials * Laser Site Spectroscopy of Transition Metal Ions in Glass * Spectroscopy of Chromium Doped Tunable Laser Materials * Spectroscopic Properties of Nd3+ Ions in LaMgAl11O19 Crystal * Spectral Study and 2.938 μm Laser Emission of Er3+ in the Y3Al5O12 Crystal * Raman-infrared Spectra and Radiationless Relaxation of Laser Crystal NdAl3(BO3)4 * A Study on HB and FLN in BaFCl0.5Br0.5:Sm2+ at 77K * Pair-pumped Upconversion Solid State Lasers * CW Upconversion Laser Action in Neodymium and Erbium doped Solids * Ultra-high Sensitive Upconversion Fluorescence of YbF3 Doped with Trace Tm3+ and Er3+ * The Growth and Properties of NYAB and EYAB Multifunctional Crystal * Study on Fluorescence and Laser Light of Er3+ in Glass * Growth and Properties of Single Crystal Fibers for Laser Materials * A Study on the Quality of Sapphire, Ruby and Ti3+ Doped Sapphire Grown by Temperature Gradient Technique (TGT) and Czochralski Technique (CZ) * The Measurement of Output Property of Ti3+ Al2O3 Laser Crystal * An Xα Study of the Laser Crystal MgF2 : V2+ * Q-switched NAB Laser * Miniature YAG Lasers * Study of High Efficiency {LiF}:{F}^-_2 Color Center Crystals * Study on the Formation Conditions and Optical Properties of (F2+)H Color Center in NaCl:OH- Crystals * Novel Spectroscopic Properties of {LiF}:{F}^+_3 - {F}_2 Mixed Color Centers Laser Crystals * Terraced Substrate Visible GaAlAs Semiconductor Lasers with a Large Optical Cavity * The Temperature Dependence of Gain Spectra, Threshold Current and Auger Recombination in InGaAsP-InP Double Heterojunction Laser diode * Time-resolved Photoluminescence and Energy Transfer of Bound Excitons in GaP:N Crystals * Optical Limiting with Semiconductors * A Critical Review of High-efficiency Crystals for Tunable Lasers * Parametric Scattering in β - BaB2O4 Crystal Induced by Picosecond Pulses * Generation of Picosecond Pulses at 193 nm by Frequency Mixing in β - BaB2O4 * Mixing Frequency Generation of 271.0 - 291.5 nm in β - BaB2O4 * Low Temperature Absorption Steps Near Ultraviolet Intrinsic Edge in Beta Barium Metaborate * The Growth and Properties of BaTiO3 Crystals * High-order Phenomena Accompanied with Self-pumped Phase Conjugation in BaTiO * Growth and Laser Damage Estimation of Potassium Dihydrogen Phosphate Crystals for Laser Fusion * Noncritically Phase-matched KTP for Diode-pumped Lasers (400-700 nm) * Potassium Titanyl Phosphate (KTP): Properties and New Applications * A Kind of New Defect in KTP Crystal and its SHG Enhanced Effect * Nucleation and Growth of the Non-linear Optical Crystal Potassium Pentaborate Tetrahydrate * Quasi-periodic Oscillations in Photoinduced Conical Light Scattering from LiNbO3 : Fe Crystals * Laser Excited Photoreflectance of GaxIn1-xAs/InP Multiple Quantum Wells * Growth, Spectroscopic Properties and Applications of Doped LiNbO3 Crystals * Photorefractive and Photovoltaic Effect in Doped LiNbO3 * Recent Advances in Photorefractive Nonlinear Optics * Study on the Doubling-frequency and Anti-photorefractive Property of Heavily Magnesium-doped Lithium-rich Lithium Niobate Crystals * A New Technique for Increasing Two-wave Mixing Gain in Photorefractive Bi12SiO20 Crystals * Experimental Proof: There Existing Another Mechanism of Photorefractive Index in Crystal Ce-SBN * Effect of Crystal Annealing on Holographic Recording in Bismuth Silicon Oxide * Two Wave Coupling in KNbO3 Photorefractive Crystal * Photorefractive Effects in Nd-Doped Ferroelectric (KxNa1-x)0.4-(SryBa1-y)0.8 Nb2O6 Single Crystal * High Pressure Raman Spectra and the Effect of Pressure to the Ferroelastic Phase Transition in LnP5O15 * Time-delay Four-wave Mixing with Incoherent Light in Absorption Bands Treated as a Multi-level System * Pulsed Laser Induced Dislocation Structure in Lithium Fluoride Single Crystals * Laser Spectroscopy * Nonclassical Radiation from Single-atom Oscillators * Laser Spectroscopic Studies of Molecules in Highly Excited Vibrational State * Investigation of the Stark Effect in Xenon Autoionizing Rydberg Series with the Use of Coherent Tunable XUV Radiation * Laser Spectroscopy of Autoionising 5 dnf J = 4.5 Rydberg Series of Ba I * Resonance Photoionization Spectroscopy of Atoms: Autoionization and Highly Excited States of Kr and U * Stark Spectra of Strontium and Calcium Atoms * Observation of Bidirectional Stimulated Radiation at 330 nm, 364 nm and 718 nm with 660 nm Laser Pumping in Sodium Vapour * Study of Molecular Rydberg States and their Discriminations in Na2 * The Measurement of the High Excited Spectra of Samarium by using Stepwise Laser Excitation Method * Product Analysis in the Reaction of the Two-photon Excited Xe(5p56p) States with Freons * Photoionization Spectra of Ca and Sr Atoms above the Classical Field-ionization Threshold * Effect of Medium Background on the Hydrogen Spectrum * Photoemission and Photoelectron Spectra from Autoionizing Atoms in Strong Laser Field * Natural Radiative Lifetime Measurements of High-lying States of Samarium * Two-step Laser Excitation of nf Rydberg States in Neutral Al and Observation of Stark Effect * Measurements of Excited Spectra of the Refractory Metal Elements using Discharge Synchronized with the Laser Pulse * Multiphoton Ionization of Atomic Lead at 1.06μ * Kinetic Processes in the Electron-beam pumped KrF Laser * Laser-induced Fluorescence of Zn2 Excimer * Calculation of Transition Intensity in Heteronuclear Dimer NaK: Comparison with Experiment * Laser-induced Fluorescence of CCl2 Carbene * Study of Multiphoton Ionization Spectrum of Benzene and Two-photon Absorption Cross Section * Dicke Narrowing of N2O Linewidth Perturbed by N2 at 10 μm Band * Polyatomic Molecular Ions Studied by Laser Photodissociation Spectroscopy * Transverse-optically Pumped Ultraviolet S2 Laser * Multiphoton Ionization of Propanal by High Power Laser * UV MPI Mass Spectroscopy and Dynamics of Photodissociation of SO2 * Multiphoton Ionization-fragmentation Patterns of Ethylamine and Dimethylamine Isomers * Cars Measurements of SF6 Pumped by a CO2 Laser Pulse * Angular Dependence of Phase Conjugation of CO2 Laser on SF6 Gas * Resolution of Stretching-vibrational and Translational Raman Bands of Liquid Water by Means of Polarization Four-photon Spectroscopy * Laser-produced Plasma as an Effective Source for X-Ray Spectroscopy * Rotational Structure of the Low Lying Electronic States of Samarium Monoxide * Effects of Poling and Stretching on Second-harmonic Generation in Amorphous Vinylidene Cyanide/Vinyl Acetate Copolymer * Laser-induced Spectroscopy of Cardiovascular Tissues * Laser-excited Malignancy Autofluorescence for Tumour Malignancy Investigation and its Origin * A Study on Several Hematoporphyrin Derivatives by Time-resolved Spectroscopy * Research on Strong Field Processes with a Subpicosecond 400 GW Ultraviolet Source * Growth, Decay and Quenching of Stimulated Raman Scattering in Transparent Liquid Droplets * Layer Condensed Ammonia Studied by Photoacoustic Spectroscopy * High Efficiency Raman Conversion of XeCl Laser Radiation in Lead Vapor * Combined Effect of Stimulated Scattering and Phase Modulation on Generation of Supercontinum * Resonant Multiwave Mixing in Sodium Vapor * High Pressure Brillouin Scattering in Liquid Toluene * Optical Nonlinearities and Bistability in Gold Colloid * Sum-frequency Generation for Surface Vibrational Spectroscopy * Optical Studies of Molecule/Surface Interactions * Optical Second Harmonic Generation with Coupled Surface Plasmons from a Multi-layer Silver/Quartz Grating * Evidence of Silver Cluster and its Role in Surface Enhanced Raman Scattering (SERS) * Study on Cold-evaporated Silver Surfaces with Second-harmonic-generation * Study of Optical Second-harmonic-generation at Metal Surface with Polarization States * Spectroscopic Studies of J-Aggregates of Pseudoisocyanine in Molecular Monolayers in the Range 300 to 20 K * Study of Polymerization of Langmuir-Blodgett Monolayer by Surface Enhanced Raman Scattering * Dynamics of Laser-induced Etching of Si(III) Surface of Chlorine * Fourier Transform Heterodyne Spectroscopy of Liquid Interfaces * Generation of High Power UV Femtosecond Pulses * Femtosecond Photon Echoes * Transition Radiation of Femtosecond Optical Pulses * Observation of DFWN in a Saturable Absorber inside the CPM Ring Dye Laser Cavity * Study on the Induced Spectral Superbroadening of Ultrafast Laser Pulse in a Nonlinear Medium * Laser Cooling and Trapping of Atoms * Femtosecond Absorption Spectroscopy of Primary Processes in Bacterial Photosynthesis Reaction Centers * Observation of the Motion of Slow Atoms in a Standing Wave Field * The Interrelation between the Optical Properties and the MBE Growth Control of Quantum Well Structures * Ionic Excimers * Optical SHG Study on Polymerization of Langmuir-Blodgett Molecular Layers * Weak Localization of Light * Statistical Fragmentation Patterns of Metastable Ion: Comparison with Experiment * Oxygeneration Reaction of Cerium with XeCl Laser * Measurement of Verdet Coefficient and Magneto-optic Spectroscopy in terms of Beats * Study on Rhodamine 6G/Xylene and Red B Laser Dye Mixture System * Ultranarrow Absorption Resonances of Cold Particles and their Application in Spectroscopy and Optical Frequency Standards * The Dynamics of Ion Clouds in Paul Traps: Implications for Frequency Standard Applications * Frequency Stability Measurement of Zeeman Stabilized He-Ne Laser * Multi-wavelength CW He-Ne Laser and its Frequency Stabilization * Efficient Isotope Separation using Semiconductor Lasers * Multi-beam Circularly Polarized Holography * Ring Laser Opticity Meter * Improved Rademacher Functions and Rademacher Transform * Note

Quasi-supercontinuum source in the extreme ultraviolet using multiple frequency combs from high-harmonic generation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wünsche, Martin; Fuchs, Silvio; Aull, Stefan

A quasi-supercontinuum source in the extreme ultraviolet (XUV) is demonstrated using a table-top femtosecond laser and a tunable optical parametric amplifier (OPA) as a driver for high-harmonic generation (HHG). The harmonic radiation, which is usually a comb of odd multiples of the fundamental frequency, is generated by near-infrared (NIR) laser pulses from the OPA. A quasi-continuous XUV spectrum in the range of 30 to 100 eV is realized by averaging over multiple harmonic comb spectra with slightly different fundamental frequencies and thus different spectral spacing between the individual harmonics. The driving laser wavelength is swept automatically during an averaging timemore » period. With a total photon flux of 4×10 9 photons/s in the range of 30 eV to 100 eV and 1×10 7 photons/s in the range of 100 eV to 200 eV, the resulting quasi-supercontinuum XUV source is suited for applications such as XUV coherence tomography (XCT) or near-edge absorption fine structure spectroscopy (NEXAFS).« less

Quasi-supercontinuum source in the extreme ultraviolet using multiple frequency combs from high-harmonic generation

DOE PAGES

Wünsche, Martin; Fuchs, Silvio; Aull, Stefan; ...

2017-03-16

A quasi-supercontinuum source in the extreme ultraviolet (XUV) is demonstrated using a table-top femtosecond laser and a tunable optical parametric amplifier (OPA) as a driver for high-harmonic generation (HHG). The harmonic radiation, which is usually a comb of odd multiples of the fundamental frequency, is generated by near-infrared (NIR) laser pulses from the OPA. A quasi-continuous XUV spectrum in the range of 30 to 100 eV is realized by averaging over multiple harmonic comb spectra with slightly different fundamental frequencies and thus different spectral spacing between the individual harmonics. The driving laser wavelength is swept automatically during an averaging timemore » period. With a total photon flux of 4×10 9 photons/s in the range of 30 eV to 100 eV and 1×10 7 photons/s in the range of 100 eV to 200 eV, the resulting quasi-supercontinuum XUV source is suited for applications such as XUV coherence tomography (XCT) or near-edge absorption fine structure spectroscopy (NEXAFS).« less

Broadband Transmission EPR Spectroscopy

PubMed Central

Hagen, Wilfred R.

2013-01-01

EPR spectroscopy employs a resonator operating at a single microwave frequency and phase-sensitive detection using modulation of the magnetic field. The X-band spectrometer is the general standard with a frequency in the 9–10 GHz range. Most (bio)molecular EPR spectra are determined by a combination of the frequency-dependent electronic Zeeman interaction and a number of frequency-independent interactions, notably, electron spin – nuclear spin interactions and electron spin – electron spin interactions, and unambiguous analysis requires data collection at different frequencies. Extant and long-standing practice is to use a different spectrometer for each frequency. We explore the alternative of replacing the narrow-band source plus single-mode resonator with a continuously tunable microwave source plus a non-resonant coaxial transmission cell in an unmodulated external field. Our source is an arbitrary wave digital signal generator producing an amplitude-modulated sinusoidal microwave in combination with a broadband amplifier for 0.8–2.7 GHz. Theory is developed for coaxial transmission with EPR detection as a function of cell dimensions and materials. We explore examples of a doublet system, a high-spin system, and an integer-spin system. Long, straigth, helical, and helico-toroidal cells are developed and tested with dilute aqueous solutions of spin label hydroxy-tempo. A detection limit of circa 5 µM HO-tempo in water at 800 MHz is obtained for the present setup, and possibilities for future improvement are discussed. PMID:23555819

Vibrational Sum Frequency Generation Spectroscopy Study of Hydrous Species in Soda Lime Silica Float Glass.

PubMed

Luo, Jiawei; Banerjee, Joy; Pantano, Carlo G; Kim, Seong H

2016-06-21

It is generally accepted that the mechanical properties of soda lime silica (SLS) glass can be affected by the interaction between sodium ions and hydrous species (silanol groups and water molecules) in its surface region. While the amount of these hydrous species can be estimated from hydrogen profiles and infrared spectroscopy, their chemical environment in the glass network is still not well understood. This work employed vibrational sum frequency generation (SFG) spectroscopy to investigate the chemical environment of hydrous species in the surface region of SLS float glass. SLS float glass shows sharp peaks in the OH stretching vibration region in SFG spectra, while the OH stretch peaks of glasses that do not have leachable sodium ions and the OH peaks of water molecules in condensed phases are normally broad due to fast hydrogen bonding dynamics. The hydrous species responsible for the sharp SFG peaks for the SLS float glass were found to be thermodynamically more stable than physisorbed water molecules, did not exchange with D2O, and were associated with the sodium concentration gradient in the dealkalized subsurface region. These results suggested that the hydrous species reside in static solvation shells defined by the silicate network with relatively slow hydrogen bonding dynamics, compared to physisorbed water layers on top of the glass surface. A putative radial distribution of the hydrous species within the SLS glass network was estimated based on the OH SFG spectral features, which could be compared with theoretical distributions calculated from computational simulations.

Monitoring Meso-Scale Ordering of Cellulose in Intact Plant Cell Walls Using Sum Frequency Generation Spectroscopy1[C][W][OPEN

PubMed Central

Park, Yong Bum; Lee, Christopher M.; Koo, Bon-Wook; Park, Sunkyu; Cosgrove, Daniel J.; Kim, Seong H.

2013-01-01

Sum frequency generation (SFG) vibration spectroscopy can selectively detect crystalline cellulose without spectral interference from cell wall matrix components. Here, we show that the cellulose SFG spectrum is sensitive to cellulose microfibril alignment and packing within the cell wall. SFG intensity at 2,944 cm−1 correlated well with crystalline cellulose contents of various regions of the Arabidopsis (Arabidopsis thaliana) inflorescence, while changes in the 3,320/2,944 cm−1 intensity ratio suggest subtle changes in cellulose ordering as tissues mature. SFG analysis of two cellulose synthase mutants (irx1/cesa8 and irx3/cesa7) indicates a reduction in cellulose content without evidence of altered cellulose structure. In primary cell walls of Arabidopsis, cellulose exhibited a characteristic SFG peak at 2,920 and 3,320 cm−1, whereas in secondary cell walls, it had peaks at 2,944 and 3,320 cm−1. Starch (amylose) gave an SFG peak at 2,904 cm−1 (CH methine) whose intensity increased with light exposure prior to harvest. Selective removal of matrix polysaccharides from primary cell walls by acid hydrolysis resulted in an SFG spectrum resembling that of secondary wall cellulose. Our results show that SFG spectroscopy is sensitive to the ordering of cellulose microfibrils in plant cell walls at the meso scale (nm to μm) that is important for cell wall architecture but cannot be probed by other spectroscopic or diffraction techniques. PMID:23995148

Broad-Bandwidth Chiral Sum Frequency Generation Spectroscopy for Probing the Kinetics of Proteins at Interfaces

PubMed Central

2016-01-01

The kinetics of proteins at interfaces plays an important role in biological functions and inspires solutions to fundamental problems in biomedical sciences and engineering. Nonetheless, due to the lack of surface-specific and structural-sensitive biophysical techniques, it still remains challenging to probe protein kinetics in situ and in real time without the use of spectroscopic labels at interfaces. Broad-bandwidth chiral sum frequency generation (SFG) spectroscopy has been recently developed for protein kinetic studies at interfaces by tracking the chiral vibrational signals of proteins. In this article, we review our recent progress in kinetic studies of proteins at interfaces using broad-bandwidth chiral SFG spectroscopy. We illustrate the use of chiral SFG signals of protein side chains in the C–H stretch region to monitor self-assembly processes of proteins at interfaces. We also present the use of chiral SFG signals from the protein backbone in the N–H stretch region to probe the real-time kinetics of proton exchange between protein and water at interfaces. In addition, we demonstrate the applications of spectral features of chiral SFG that are typical of protein secondary structures in both the amide I and the N–H stretch regions for monitoring the kinetics of aggregation of amyloid proteins at membrane surfaces. These studies exhibit the power of broad-bandwidth chiral SFG to study protein kinetics at interfaces and the promise of this technique in research areas of surface science to address fundamental problems in biomedical and material sciences. PMID:26196215

Ordered adsorption of coagulation factor XII on negatively charged polymer surfaces probed by sum frequency generation vibrational spectroscopy.

PubMed

Chen, Xiaoyun; Wang, Jie; Paszti, Zoltan; Wang, Fulin; Schrauben, Joel N; Tarabara, Volodymyr V; Schmaier, Alvin H; Chen, Zhan

2007-05-01

Electrostatic interactions between negatively charged polymer surfaces and factor XII (FXII), a blood coagulation factor, were investigated by sum frequency generation (SFG) vibrational spectroscopy, supplemented by several analytical techniques including attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), quartz crystal microbalance (QCM), zeta-potential measurement, and chromogenic assay. A series of sulfonated polystyrenes (sPS) with different sulfonation levels were synthesized as model surfaces with different surface charge densities. SFG spectra collected from FXII adsorbed onto PS and sPS surfaces with different surface charge densities showed remarkable differences in spectral features and especially in spectral intensity. Chromogenic assay experiments showed that highly charged sPS surfaces induced FXII autoactivation. ATR-FTIR and QCM results indicated that adsorption amounts on the PS and sPS surfaces were similar even though the surface charge densities were different. No significant conformational change was observed from FXII adsorbed onto surfaces studied. Using theoretical calculations, the possible contribution from the third-order nonlinear optical effect induced by the surface electric field was evaluated, and it was found to be unable to yield the SFG signal enhancement observed. Therefore it was concluded that the adsorbed FXII orientation and ordering were the main reasons for the remarkable SFG amide I signal increase on sPS surfaces. These investigations indicate that negatively charged surfaces facilitate or induce FXII autoactivation on the molecular level by imposing specific orientation and ordering on the adsorbed protein molecules.

Monitoring meso-scale ordering of cellulose in intact plant cell walls using sum frequency generation spectroscopy.

PubMed

Park, Yong Bum; Lee, Christopher M; Koo, Bon-Wook; Park, Sunkyu; Cosgrove, Daniel J; Kim, Seong H

2013-10-01

Sum frequency generation (SFG) vibration spectroscopy can selectively detect crystalline cellulose without spectral interference from cell wall matrix components. Here, we show that the cellulose SFG spectrum is sensitive to cellulose microfibril alignment and packing within the cell wall. SFG intensity at 2,944 cm(-1) correlated well with crystalline cellulose contents of various regions of the Arabidopsis (Arabidopsis thaliana) inflorescence, while changes in the 3,320/2,944 cm(-1) intensity ratio suggest subtle changes in cellulose ordering as tissues mature. SFG analysis of two cellulose synthase mutants (irx1/cesa8 and irx3/cesa7) indicates a reduction in cellulose content without evidence of altered cellulose structure. In primary cell walls of Arabidopsis, cellulose exhibited a characteristic SFG peak at 2,920 and 3,320 cm(-1), whereas in secondary cell walls, it had peaks at 2,944 and 3,320 cm(-1). Starch (amylose) gave an SFG peak at 2,904 cm(-1) (CH methine) whose intensity increased with light exposure prior to harvest. Selective removal of matrix polysaccharides from primary cell walls by acid hydrolysis resulted in an SFG spectrum resembling that of secondary wall cellulose. Our results show that SFG spectroscopy is sensitive to the ordering of cellulose microfibrils in plant cell walls at the meso scale (nm to μm) that is important for cell wall architecture but cannot be probed by other spectroscopic or diffraction techniques.

Femtosecond optical parametric oscillators toward real-time dual-comb spectroscopy

NASA Astrophysics Data System (ADS)

Jin, Yuwei; Cristescu, Simona M.; Harren, Frans J. M.; Mandon, Julien

2015-04-01

We demonstrate mid-infrared dual-comb spectroscopy with an optical parametric oscillator (OPO) toward real-time field measurement. A singly resonant OPO based on a MgO-doped periodically poled lithium niobate (PPLN) crystal is demonstrated. Chirped mirrors are used to compensate the dispersion caused by the optical cavity and the crystal. A low threshold of 17 mW has been achieved. The OPO source generates a tunable idler frequency comb between 2.7 and 4.7 μm. Dual-comb spectroscopy is achieved by coupling two identical Yb-fiber mode-locked lasers to this OPO with slightly different repetition frequencies. A measured absorption spectrum of methane is presented with a spectral bandwidth of , giving an instrumental resolution of . In addition, a second OPO containing two MgO-doped PPLN crystals in a singly resonant ring cavity is demonstrated. As such, this OPO generates two idler combs (average power up to 220 mW), covering a wavelength range between 2.7 and 4.2 μm, from which a mid-infrared dual-comb Fourier transform spectrometer is constructed. By detecting the heterodyned signal between the two idler combs, broadband spectra of molecular gases can be observed over a spectral bandwidth of more than . This special cavity design allows the spectral resolution to be improved to without locking the OPO cavity, indicating that this OPO represents an ideal high-power broadband mid-infrared source for real-time gas sensing.

Continuous-wave optical parametric oscillators on their way to the terahertz range

NASA Astrophysics Data System (ADS)

Sowade, Rosita; Breunig, Ingo; Kiessling, Jens; Buse, Karsten

2010-02-01

Continuous-wave optical parametric oscillators (OPOs) are known to be working horses for spectroscopy in the near- and mid-infrared. However, strong absorption in nonlinear media like lithium niobate complicates the generation of far-infrared light. This absorption leads to pump thresholds vastly exceeding the power of standard pump lasers. Our first approach was, therefore, to combine the established technique of photomixing with optical parametric oscillators. Here, two OPOs provide one wave each, with a tunable difference frequency. These waves are combined to a beat signal as a source for photomixers. Terahertz radiation between 0.065 and 1.018 THz is generated with powers in the order of nanowatts. To overcome the upper frequency limit of the opto-electronic photomixers, terahertz generation has to rely entirely on optical methods. Our all-optical approach, getting around the high thresholds for terahertz generation, is based on cascaded nonlinear processes: the resonantly enhanced signal field, generated in the primary parametric process, is intense enough to act as the pump for a secondary process, creating idler waves with frequencies in the terahertz regime. The latter ones are monochromatic and tunable with detected powers of more than 2 μW at 1.35 THz. Thus, continuous-wave optical parametric oscillators have entered the field of terahertz photonics.

Linear and Nonlinear Molecular Spectroscopy with Laser Frequency Combs

NASA Astrophysics Data System (ADS)

Picque, Nathalie

2013-06-01

The regular pulse train of a mode-locked femtosecond laser can give rise to a comb spectrum of millions of laser modes with a spacing precisely equal to the pulse repetition frequency. Laser frequency combs were conceived a decade ago as tools for the precision spectroscopy of atomic hydrogen. They are now becoming enabling tools for an increasing number of applications, including molecular spectroscopy. Recent experiments of multi-heterodyne frequency comb Fourier transform spectroscopy (also called dual-comb spectroscopy) have demonstrated that the precisely spaced spectral lines of a laser frequency comb can be harnessed for new techniques of linear absorption spectroscopy. The first proof-of-principle experiments have demonstrated a very exciting potential of dual-comb spectroscopy without moving parts for ultra-rapid and ultra-sensitive recording of complex broad spectral bandwidth molecular spectra. Compared to conventional Michelson-based Fourier transform spectroscopy, recording times could be shortened from seconds to microseconds, with intriguing prospects for spectroscopy of short lived transient species. The resolution improves proportionally to the measurement time. Therefore longer recordings allow high resolution spectroscopy of molecules with extreme precision, since the absolute frequency of each laser comb line can be known with the accuracy of an atomic clock. Moreover, since laser frequency combs involve intense ultrashort laser pulses, nonlinear interactions can be harnessed. Broad spectral bandwidth ultra-rapid nonlinear molecular spectroscopy and imaging with two laser frequency combs is demonstrated with coherent Raman effects and two-photon excitation. Real-time multiplex accessing of hyperspectral images may dramatically expand the range of applications of nonlinear microscopy. B. Bernhardt et al., Nature Photonics 4, 55-57 (2010); A. Schliesser et al. Nature Photonics 6, 440-449 (2012); T. Ideguchi et al. arXiv:1201.4177 (2012) T. Ideguchi et al., Optics letters 37, 4498-4500 (2012); T. Ideguchi et al. arXiv:1302.2414 (2013)

Dual THz comb spectroscopy

NASA Astrophysics Data System (ADS)

Yasui, Takeshi

2017-08-01

Optical frequency combs are innovative tools for broadband spectroscopy because a series of comb modes can serve as frequency markers that are traceable to a microwave frequency standard. However, a mode distribution that is too discrete limits the spectral sampling interval to the mode frequency spacing even though individual mode linewidth is sufficiently narrow. Here, using a combination of a spectral interleaving and dual-comb spectroscopy in the terahertz (THz) region, we achieved a spectral sampling interval equal to the mode linewidth rather than the mode spacing. The spectrally interleaved THz comb was realized by sweeping the laser repetition frequency and interleaving additional frequency marks. In low-pressure gas spectroscopy, we achieved an improved spectral sampling density of 2.5 MHz and enhanced spectral accuracy of 8.39 × 10-7 in the THz region. The proposed method is a powerful tool for simultaneously achieving high resolution, high accuracy, and broad spectral coverage in THz spectroscopy.

OH Production Enhancement in Bubbling Pulsed Discharges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lungu, Cristian P.; Porosnicu, Corneliu; Jepu, Ionut

2010-10-13

The generation of active species, such as H{sub 2}O{sub 2}, O{sup *}, OH*, HO{sub 2}*, O{sub 3}, N{sub 2}{sup *}, etc, produced in aqueous solutions by HV pulsed discharges was studied in order to find the most efficient way in waste water treatment taking into account that these species are almost stronger oxidizers than ozone. Plasma was generated inside gas bubbles formed by the argon, air and oxygen gas flow between the special designed electrodes. The pulse width and pulse frequency influence was studied in order to increase the efficiency of the OH active species formation. The produced active speciesmore » were investigated by optical emission spectroscopy and correlated with electrical parameters of the discharges (frequency, pulse width, amplitude, and rise and decay time).« less

Detection of amide I signals of interfacial proteins in situ using SFG.

PubMed

Wang, Jie; Even, Mark A; Chen, Xiaoyun; Schmaier, Alvin H; Waite, J Herbert; Chen, Zhan

2003-08-20

In this Communication, we demonstrate the novel observation that it is feasible to collect amide signals from polymer/protein solution interfaces in situ using sum frequency generation (SFG) vibrational spectroscopy. Such SFG amide signals allow for acquisition of more detailed molecular level information of entire interfacial protein structures. Proteins investigated include bovine serum albumin, mussel protein mefp-2, factor XIIa, and ubiquitin. Our studies indicate that different proteins generate different SFG amide signals at the polystyrene/protein solution interface, showing that they have different interfacial coverage, secondary structure, or orientation.

Dielectrophoretic spectroscopy using a microscopic electrode array

NASA Astrophysics Data System (ADS)

Kirmani, Syed Abdul Mannan; Gudagunti, Fleming Dackson; Velmanickam, Logeeshan; Nawarathna, Dharmakeerthi; Lima, Ivan T.

2017-02-01

Dielectrophoresis (DEP) is a commonly used technique in biomedical engineering to manipulate biomolecules. DEP is defined as the force acting on dielectric particles when they are exposed to non-uniform electric fields. DEP effect can be divided in three categories: positive (dielectric particles are attracted to the electrodes), negative, and zero force DEP. The cross-over frequency is the frequency in which the DEP force is equal to zero. The cross-over frequency depends on the conductivity and the permittivity of the particles and of the suspended medium. The DEP cross-over frequency has been utilized in detecting/quantifying biomolecules. A manual procedure is commonly used to estimate the cross-over frequency of biomolecules. Therefore, the accuracy of this detection method is significantly limited. To address this issue, we designed and tested an automated procedure to carry out DEP spectroscopy in dielectric particles dissolved in a biological buffer solution. Our method efficiently measures the effect of the DEP force through a live video feed from the microscope camera and performs real-time image processing. It records the change in the fluorescence emission as the system automatically scans the electric frequency of the function generator over a specified time interval. We demonstrated the effectiveness of the method by extracting the crossover frequencies and the DEP spectrum of polystyrene beads with blue color dye (1000 nm diameter) and green fluorescent polystyrene beads with 500 nm diameter using this procedure. This approach can lead to the development of a biosensor with significantly higher sensitivity than existing detection methods.

Review of GaN-based devices for terahertz operation

NASA Astrophysics Data System (ADS)

Ahi, Kiarash

2017-09-01

GaN provides the highest electron saturation velocity, breakdown voltage, operation temperature, and thus the highest combined frequency-power performance among commonly used semiconductors. The industrial need for compact, economical, high-resolution, and high-power terahertz (THz) imaging and spectroscopy systems are promoting the utilization of GaN for implementing the next generation of THz systems. As it is reviewed, the mentioned characteristics of GaN together with its capabilities of providing high two-dimensional election densities and large longitudinal optical phonon of ˜90 meV make it one of the most promising semiconductor materials for the future of the THz emitters, detectors, mixers, and frequency multiplicators. GaN-based devices have shown capabilities of operation in the upper THz frequency band of 5 to 12 THz with relatively high photon densities in room temperature. As a result, THz imaging and spectroscopy systems with high resolution and deep depth of penetration can be realized through utilizing GaN-based devices. A comprehensive review of the history and the state of the art of GaN-based electronic devices, including plasma heterostructure field-effect transistors, negative differential resistances, hetero-dimensional Schottky diodes, impact avalanche transit times, quantum-cascade lasers, high electron mobility transistors, Gunn diodes, and tera field-effect transistors together with their impact on the future of THz imaging and spectroscopy systems is provided.

Dielectric-spectroscopy approach to ferrofluid nanoparticle clustering induced by an external electric field.

PubMed

Rajnak, Michal; Kurimsky, Juraj; Dolnik, Bystrik; Kopcansky, Peter; Tomasovicova, Natalia; Taculescu-Moaca, Elena Alina; Timko, Milan

2014-09-01

An experimental study of magnetic colloidal particles cluster formation induced by an external electric field in a ferrofluid based on transformer oil is presented. Using frequency domain isothermal dielectric spectroscopy, we study the influence of a test cell electrode separation distance on a low-frequency relaxation process. We consider the relaxation process to be associated with an electric double layer polarization taking place on the particle surface. It has been found that the relaxation maximum considerably shifts towards lower frequencies when conducting the measurements in the test cells with greater electrode separation distances. As the electric field intensity was always kept at a constant value, we propose that the particle cluster formation induced by the external ac electric field accounts for that phenomenon. The increase in the relaxation time is in accordance with the Schwarz theory of electric double layer polarization. In addition, we analyze the influence of a static electric field generated by dc bias voltage on a similar shift in the relaxation maximum position. The variation of the dc electric field for the hysteresis measurements purpose provides understanding of the development of the particle clusters and their decay. Following our results, we emphasize the utility of dielectric spectroscopy as a simple, complementary method for detection and study of clusters of colloidal particles induced by external electric field.

Homogeneous and inhomogeneous broadenings and the Voigt line shapes in the phase-resolved and intensity sum-frequency generation vibrational spectroscopy.

PubMed

Chen, Shun-Li; Fu, Li; Gan, Wei; Wang, Hong-Fei

2016-01-21

In this report, we show that the ability to measure the sub-1 cm(-1) resolution phase-resolved and intensity high-resolution broadband sum frequency generation vibrational spectra of the -CN stretch vibration of the Langmuir-Blodgett (LB) monolayer of the 4-n-octyl-4'-cyanobiphenyl (8CB) on the z-cut α-quartz surface allows the direct comparison and understanding of the homogeneous and inhomogeneous broadenings in the imaginary and intensity SFG vibrational spectral line shapes in detail. The difference of the full width at half maximum (FWHM) of the imaginary and intensity sum-frequency generation vibrational spectroscopy spectra of the same vibrational mode is the signature of the Voigt line shape and it measures the relative contribution to the overall line shape from the homogeneous and inhomogeneous broadenings in SFG vibrational spectra. From the phase-resolved and intensity spectra, we found that the FWHM of the 2238.00 ± 0.02 cm(-1) peak in the phase-resolved imaginary and intensity spectra is 19.2 ± 0.2 cm(-1) and 21.6 ± 0.4 cm(-1), respectively, for the -CN group of the 8CB LB monolayer on the z-cut α-quartz crystal surface. The FWHM width difference of 2.4 cm(-1) agrees quantitatively with a Voigt line shape with a homogeneous broadening half width of Γ = 5.29 ± 0.08 cm(-1) and an inhomogeneous standard derivation width Δω = 5.42 ± 0.07 cm(-1). These results shed new lights on the understanding and interpretation of the line shapes of both the phase-resolved and the intensity SFG vibrational spectra, as well as other incoherent and coherent spectroscopic techniques in general.

STUDIES OF THE ORIGIN OF HIGH-FREQUENCY QUASI-PERIODIC OSCILLATIONS OF MASS-ACCRETING BLACK HOLES IN X-RAY BINARIES WITH NEXT-GENERATION X-RAY TELESCOPES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beheshtipour, Banafsheh; Hoormann, Janie K.; Krawczynski, Henric, E-mail: b.beheshtipour@wustl.edu

Observations with RXTE ( Rossi X-ray Timing Explorer ) revealed the presence of high-frequency quasi-periodic oscillations (HFQPOs) of the X-ray flux from several accreting stellar-mass black holes. HFQPOs (and their counterparts at lower frequencies) may allow us to study general relativity in the regime of strong gravity. However, the observational evidence today does not yet allow us to distinguish between different HFQPO models. In this paper we use a general-relativistic ray-tracing code to investigate X-ray timing spectroscopy and polarization properties of HFQPOs in the orbiting Hotspot model. We study observational signatures for the particular case of the 166 Hz quasi-periodicmore » oscillation (QPO) in the galactic binary GRS 1915+105. We conclude with a discussion of the observability of spectral signatures with a timing-spectroscopy experiment such as the LOFT ( Large Observatory for X-ray Timing ) and polarization signatures with space-borne X-ray polarimeters such as IXPE ( Imaging X-ray Polarimetry Explorer ), PolSTAR ( Polarization Spectroscopic Telescope Array ), PRAXyS ( Polarimetry of Relativistic X-ray Sources ), or XIPE ( X-ray Imaging Polarimetry Explorer ). A mission with high count rate such as LOFT would make it possible to get a QPO phase for each photon, enabling the study of the QPO-phase-resolved spectral shape and the correlation between this and the flux level. Owing to the short periods of the HFQPOs, first-generation X-ray polarimeters would not be able to assign a QPO phase to each photon. The study of QPO-phase-resolved polarization energy spectra would thus require simultaneous observations with a first-generation X-ray polarimeter and a LOFT -type mission.« less

Characterization of a commercial software defined radio as high frequency lock-in amplifier for FM spectroscopy.

PubMed

Mahnke, Peter

2018-01-01

A commercial software defined radio based on a Rafael Micro R820T2 tuner is characterized for the use as a high-frequency lock-in amplifier for frequency modulation spectroscopy. The sensitivity limit of the receiver is 1.6 nV/Hz. Frequency modulation spectroscopy is demonstrated on the 6406.69 cm -1 absorption line of carbon monoxide.

Characterization of a commercial software defined radio as high frequency lock-in amplifier for FM spectroscopy

NASA Astrophysics Data System (ADS)

Mahnke, Peter

2018-01-01

A commercial software defined radio based on a Rafael Micro R820T2 tuner is characterized for the use as a high-frequency lock-in amplifier for frequency modulation spectroscopy. The sensitivity limit of the receiver is 1.6 nV/√{Hz }. Frequency modulation spectroscopy is demonstrated on the 6406.69 cm-1 absorption line of carbon monoxide.

THz spectroscopy of D2H+

NASA Astrophysics Data System (ADS)

Yu, S.; Pearson, J. C.; Amano, T.; Matsushima, F.

2017-01-01

We extended the measurements of the rotational transitions of D2H+ up to 3 THz by using the JPL frequency multiplier chains and a TuFIR system at Toyama. D2H+ was generated in an extended negative glow discharge cell cooled to liquid nitrogen temperature. We observed five new THz lines. All the available rotational transition frequencies together with the combination differences derived from the three fundamental bands were subject to least square analysis to determine the molecular constants. New THz measurements are definitely useful for better characterization of spectroscopic properties. The improved molecular constants provide better predictions of other unobserved rotational transitions.

Orientations of nonlocal vibrational modes from combined experimental and theoretical sum frequency spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chase, Hilary M.; Chen, Shunli; Fu, Li

2017-09-01

Inferring molecular orientations from vibrational sum frequency generation (SFG) spectra is challenging in polarization combinations that result in low signal intensities, or when the local point group symmetry approximation fails. While combining experiments with density functional theory (DFT) could overcome this problem, the scope of the combined method has yet to be established. Here, we assess its feasibility of determining the distributions of molecular orientations for one monobasic ester, two epoxides and three alcohols at the vapor/fused silica interface. We find that molecular orientations of nonlocal vibrational modes cannot be determined using polarization-resolved SFG measurements alone.

Non-Destructive Testing with Atmospheric Pressure Radio-Frequency Plasma

NASA Astrophysics Data System (ADS)

May, A.; Andarawis, E.

2007-03-01

We summarize our recent work using radio-frequency (RF) atmospheric pressure plasma (APP) for non-destructive evaluation (NDE), specifically for: (1) Clearance sensing (0-5mm) on rotating components, and (2) Generation of broadband ultrasound in air at 900kHz. RF-APP showed potential in both of these common NDE requirements, but further work is required to better characterize and optimize the performance of the new techniques. Application of RF-APP to other NDE disciplines, such as plasma spectroscopy and gas flow measurement, is also likely to be advantageous, especially in harsh environments where existing approaches are prohibitively expensive or complex.

Selectivity enhancement in photoacoustic gas analysis via phase-sensitive detection at high modulation frequency

NASA Technical Reports Server (NTRS)

Kosterev, Anatoliy (Inventor)

2010-01-01

A method for detecting a target fluid in a fluid sample comprising a first fluid and the target fluid using photoacoustic spectroscopy (PAS), comprises a) providing a light source configured to introduce an optical signal having at least one wavelength into the fluid sample; b) modulating the optical signal at a desired modulation frequency such that the optical signal generates an acoustic signal in the fluid sample; c) measuring the acoustic signal in a resonant acoustic detector; and d) using the phase of the acoustic signal to detect the presence of the target fluid.

1998 Conference on Precision Electromagnetic Measurements Digest. Proceedings.

NASA Astrophysics Data System (ADS)

Nelson, T. L.

The following topics were dealt with: fundamental constants; caesium standards; AC-DC transfer; impedance measurement; length measurement; units; statistics; cryogenic resonators; time transfer; QED; resistance scaling and bridges; mass measurement; atomic fountains and clocks; single electron transport; Newtonian constant of gravitation; stabilised lasers and frequency measurements; cryogenic current comparators; optical frequency standards; high voltage devices and systems; international compatibility; magnetic measurement; precision power measurement; high resolution spectroscopy; DC transport standards; waveform acquisition and analysis; ion trap standards; optical metrology; quantised Hall effect; Josephson array comparisons; signal generation and measurement; Avogadro constant; microwave networks; wideband power standards; antennas, fields and EMC; quantum-based standards.

Ultrasonic standing wave preparation of a liquid cell for glucose measurements in urine by midinfrared spectroscopy and potential application to smart toilets.

PubMed

Yamamoto, Naoyuki; Kawashima, Natsumi; Kitazaki, Tomoya; Mori, Keita; Kang, Hanyue; Nishiyama, Akira; Wada, Kenji; Ishimaru, Ichiro

2018-05-01

Smart toilets could be used to monitor different components of urine in daily life for early detection of lifestyle-related diseases and prompt provision of treatment. For analysis of biological samples such as urine by midinfrared spectroscopy, thin-film samples like liquid cells are needed because of the strong absorption of midinfrared light by water. Conventional liquid cells or fixed cells are prepared based on the liquid membrane method and solution technique, but these are not quantitative and are difficult to set up and clean. We generated an ultrasonic standing wave reflection plane in a sample and produced an ultrasonic liquid cell. In this cell, the thickness of the optical path length was adjustable, as in the conventional method. The reflection plane could be generated at an arbitrary depth and internal reflected light could be detected by changing the frequency of the ultrasonic wave. We could generate refractive index boundaries using the density difference created by the ultrasonic standing wave. Creation of the reflection plane in the sample was confirmed by optical coherence tomography. Using the proposed method and midinfrared spectroscopy, we discriminated between normal urine samples spiked with glucose at different concentrations and obtained a high correlation coefficient. (2018) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

Heterodyne laser spectroscopy system

DOEpatents

Wyeth, Richard W.; Paisner, Jeffrey A.; Story, Thomas

1990-01-01

A heterodyne laser spectroscopy system utilizes laser heterodyne techniques for purposes of laser isotope separation spectroscopy, vapor diagnostics, processing of precise laser frequency offsets from a reference frequency, and provides spectral analysis of a laser beam.

Spectral purity and tunability of terahertz quantum cascade laser sources based on intracavity difference-frequency generation

PubMed Central

Consolino, Luigi; Jung, Seungyong; Campa, Annamaria; De Regis, Michele; Pal, Shovon; Kim, Jae Hyun; Fujita, Kazuue; Ito, Akio; Hitaka, Masahiro; Bartalini, Saverio; De Natale, Paolo; Belkin, Mikhail A.; Vitiello, Miriam Serena

2017-01-01

Terahertz sources based on intracavity difference-frequency generation in mid-infrared quantum cascade lasers (THz DFG-QCLs) have recently emerged as the first monolithic electrically pumped semiconductor sources capable of operating at room temperature across the 1- to 6-THz range. Despite tremendous progress in power output, which now exceeds 1 mW in pulsed and 10 μW in continuous-wave regimes at room temperature, knowledge of the major figure of merits of these devices for high-precision spectroscopy, such as spectral purity and absolute frequency tunability, is still lacking. By exploiting a metrological grade system comprising a terahertz frequency comb synthesizer, we measure, for the first time, the free-running emission linewidth (LW), the tuning characteristics, and the absolute center frequency of individual emission lines of these sources with an uncertainty of 4 × 10−10. The unveiled emission LW (400 kHz at 1-ms integration time) indicates that DFG-QCLs are well suited to operate as local oscillators and to be used for a variety of metrological, spectroscopic, communication, and imaging applications that require narrow-LW THz sources. PMID:28879235

Room temperature continuous wave, monolithic tunable THz sources based on highly efficient mid-infrared quantum cascade lasers

PubMed Central

Lu, Quanyong; Wu, Donghai; Sengupta, Saumya; Slivken, Steven; Razeghi, Manijeh

2016-01-01

A compact, high power, room temperature continuous wave terahertz source emitting in a wide frequency range (ν ~ 1–5 THz) is of great importance to terahertz system development for applications in spectroscopy, communication, sensing, and imaging. Here, we present a strong-coupled strain-balanced quantum cascade laser design for efficient THz generation based on intracavity difference frequency generation. Room temperature continuous wave emission at 3.41 THz with a side-mode suppression ratio of 30 dB and output power up to 14 μW is achieved with a wall-plug efficiency about one order of magnitude higher than previous demonstrations. With this highly efficient design, continuous wave, single mode THz emissions with a wide frequency tuning range of 2.06–4.35 THz and an output power up to 4.2 μW are demonstrated at room temperature from two monolithic three-section sampled grating distributed feedback-distributed Bragg reflector lasers. PMID:27009375

High-energy and ultra-wideband tunable terahertz source with DAST crystal via difference frequency generation

NASA Astrophysics Data System (ADS)

He, Yixin; Wang, Yuye; Xu, Degang; Nie, Meitong; Yan, Chao; Tang, Longhuang; Shi, Jia; Feng, Jiachen; Yan, Dexian; Liu, Hongxiang; Teng, Bing; Feng, Hua; Yao, Jianquan

2018-01-01

We have demonstrated a high-energy and broadly tunable monochromatic terahertz (THz) source based on difference frequency generation (DFG) in DAST crystal. A high-energy dual-wavelength optical parametric oscillator with two KTP crystals was constructed as a light source for DFG, where the effect of blue light was first observed accompanying with tunable dual-wavelength pump light due to different nonlinear processes. The THz frequency was tuned randomly in the range of 0.3-19.6 THz. The highest energy of 870 nJ/pulse was obtained at 18.9 THz under the intense pump intensity of 247 MW/cm2. The THz energy dips above 3 THz have been analyzed and mainly attributed to the resonance absorption induced by lattice vibration in DAST crystal. The dependence of THz output on the input energy was studied experimentally, and THz output saturation was observed. Furthermore, tests of transmission spectroscopy of four typical samples were demonstrated with this ultra-wideband THz source.

Propagation of THz acoustic wave packets in GaN at room temperature

NASA Astrophysics Data System (ADS)

Maznev, A. A.; Hung, T.-C.; Yao, Y.-T.; Chou, T.-H.; Gandhi, J. S.; Lindsay, L.; Shin, H. D.; Stokes, D. W.; Forrest, R. L.; Bensaoula, A.; Sun, C.-K.; Nelson, K. A.

2018-02-01

We use femtosecond laser pulses to generate coherent longitudinal acoustic phonons at frequencies of 1-1.4 THz and study their propagation in GaN-based structures at room temperature. Two InGaN-GaN multiple-quantum-well (MQW) structures separated by a 2.3 μm-thick GaN spacer are used to simultaneously generate phonon wave packets with a central frequency determined by the period of the MQW and detect them after passing through the spacer. The measurements provide lower bounds for phonon lifetimes in GaN, which are still significantly lower than those from first principles predictions. The material Q-factor at 1 THz is found to be at least as high as 900. The measurements also demonstrate a partial specular reflection from the free surface of GaN at 1.4 THz. This work shows the potential of laser-based methods for THz range phonon spectroscopy and the promise for extending the viable frequency range of GaN-based acousto-electronic devices.

Room temperature continuous wave, monolithic tunable THz sources based on highly efficient mid-infrared quantum cascade lasers.

PubMed

Lu, Quanyong; Wu, Donghai; Sengupta, Saumya; Slivken, Steven; Razeghi, Manijeh

2016-03-24

A compact, high power, room temperature continuous wave terahertz source emitting in a wide frequency range (ν~1-5 THz) is of great importance to terahertz system development for applications in spectroscopy, communication, sensing, and imaging. Here, we present a strong-coupled strain-balanced quantum cascade laser design for efficient THz generation based on intracavity difference frequency generation. Room temperature continuous wave emission at 3.41 THz with a side-mode suppression ratio of 30 dB and output power up to 14 μW is achieved with a wall-plug efficiency about one order of magnitude higher than previous demonstrations. With this highly efficient design, continuous wave, single mode THz emissions with a wide frequency tuning range of 2.06-4.35 THz and an output power up to 4.2 μW are demonstrated at room temperature from two monolithic three-section sampled grating distributed feedback-distributed Bragg reflector lasers.

Heterodyne laser spectroscopy system

DOEpatents

Wyeth, Richard W.; Paisner, Jeffrey A.; Story, Thomas

1989-01-01

A heterodyne laser spectroscopy system utilizes laser heterodyne techniques for purposes of laser isotope separation spectroscopy, vapor diagnostics, processing of precise laser frequency offsets from a reference frequency and the like, and provides spectral analysis of a laser beam.

Spectrally interleaved, comb-mode-resolved spectroscopy using swept dual terahertz combs

PubMed Central

Hsieh, Yi-Da; Iyonaga, Yuki; Sakaguchi, Yoshiyuki; Yokoyama, Shuko; Inaba, Hajime; Minoshima, Kaoru; Hindle, Francis; Araki, Tsutomu; Yasui, Takeshi

2014-01-01

Optical frequency combs are innovative tools for broadband spectroscopy because a series of comb modes can serve as frequency markers that are traceable to a microwave frequency standard. However, a mode distribution that is too discrete limits the spectral sampling interval to the mode frequency spacing even though individual mode linewidth is sufficiently narrow. Here, using a combination of a spectral interleaving and dual-comb spectroscopy in the terahertz (THz) region, we achieved a spectral sampling interval equal to the mode linewidth rather than the mode spacing. The spectrally interleaved THz comb was realized by sweeping the laser repetition frequency and interleaving additional frequency marks. In low-pressure gas spectroscopy, we achieved an improved spectral sampling density of 2.5 MHz and enhanced spectral accuracy of 8.39 × 10−7 in the THz region. The proposed method is a powerful tool for simultaneously achieving high resolution, high accuracy, and broad spectral coverage in THz spectroscopy. PMID:24448604

Laser frequency stabilization by combining modulation transfer and frequency modulation spectroscopy.

PubMed

Zi, Fei; Wu, Xuejian; Zhong, Weicheng; Parker, Richard H; Yu, Chenghui; Budker, Simon; Lu, Xuanhui; Müller, Holger

2017-04-01

We present a hybrid laser frequency stabilization method combining modulation transfer spectroscopy (MTS) and frequency modulation spectroscopy (FMS) for the cesium D₂ transition. In a typical pump-probe setup, the error signal is a combination of the DC-coupled MTS error signal and the AC-coupled FMS error signal. This combines the long-term stability of the former with the high signal-to-noise ratio of the latter. In addition, we enhance the long-term frequency stability with laser intensity stabilization. By measuring the frequency difference between two independent hybrid spectroscopies, we investigate the short-and long-term stability. We find a long-term stability of 7.8 kHz characterized by a standard deviation of the beating frequency drift over the course of 10 h and a short-term stability of 1.9 kHz characterized by an Allan deviation of that at 2 s of integration time.

Gas spectroscopy system with transmitters and receivers in SiGe BiCMOS for 225-273 GHz

NASA Astrophysics Data System (ADS)

Schmalz, Klaus; Rothbart, Nick; Borngräber, Johannes; Yilmaz, Selahattin Berk; Kissinger, Dietmar; Hübers, Heinz-Wilhelm

2017-10-01

This paper updates results of our work on gas spectroscopy based on transmitters (TXs) and receivers (RXs) in IHP's 0.13 μm SiGe BiCMOS technology. The improved performance of our system is shown by the absorption spectra of gaseous methanol in the range 241 - 242 GHz at 1.4 Pa, corresponding to an absorption line width of about 1 MHz. The signal-noise ratio (SNR) for the absorption line of methanol at 241.7 GHz is used as measure. The system includes two fractional-n phase-locked loops (PLLs), which allow frequency ramps for the TX and RX, and a superimposed frequency shift keying modulation (FSK) for the TX. Another option includes reference frequency ramps for the PLLs in integer-n mode, which are realized by a direct digital synthesizer (DDS). An SNR of 1515 is observed for the 241.7 GHz absorption line at 1.4 Pa. We extend our single band TX/RX system with the range 238 - 252 GHz to a multi-band system to cover the range 225 - 273 GHz. It is built by combining corresponding pairs of TXs and RXs of three frequency bands in this range. The multi-band operation allows parallel spectra acquisition for these bands. For the TXs and RXs appropriate frequency ramps are generated by their external fractional-n PLL devices.

Twisted MoSe 2 bilayers with variable local stacking and interlayer coupling revealed by low-frequency Raman spectroscopy

DOE PAGES

Puretzky, Alexander A.; Liang, Liangbo; Li, Xufan; ...

2016-01-14

Unique twisted bilayers of MoSe 2 with multiple stacking orientations and interlayer couplings in the narrow range of twist angles, 60 ± 3°, are revealed by low-frequency Raman spectroscopy and theoretical analysis. The slight deviation from 60 allows the concomitant presence of patches featuring all three high-symmetry stacking configurations (2H or AA', AB', A'B) in one unique bilayer system. In this case, the periodic arrangement of the patches and their size strongly depend on the twist angle. Ab initio modeling predicts significant changes in frequencies and intensities of low-frequency modes versus stacking and twist angle. Experimentally, the variable stacking andmore » coupling across the interface is revealed by the appearance of two breathing modes corresponding to the mixture of the high-symmetry stacking configurations and unaligned regions of monolayers. Only one breathing mode is observed outside the narrow range of twist angles. This indicates a stacking transition to unaligned monolayers with mismatched atom registry without the in-plane restoring force required to generate a shear mode. As a result, the variable interlayer coupling and spacing in transition metal dichalcogenide bilayers revealed in this study may provide a new platform for optoelectronic applications of these materials.« less

Twisted MoSe 2 bilayers with variable local stacking and interlayer coupling revealed by low-frequency Raman spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Puretzky, Alexander A.; Liang, Liangbo; Li, Xufan

Unique twisted bilayers of MoSe 2 with multiple stacking orientations and interlayer couplings in the narrow range of twist angles, 60 ± 3°, are revealed by low-frequency Raman spectroscopy and theoretical analysis. The slight deviation from 60 allows the concomitant presence of patches featuring all three high-symmetry stacking configurations (2H or AA', AB', A'B) in one unique bilayer system. In this case, the periodic arrangement of the patches and their size strongly depend on the twist angle. Ab initio modeling predicts significant changes in frequencies and intensities of low-frequency modes versus stacking and twist angle. Experimentally, the variable stacking andmore » coupling across the interface is revealed by the appearance of two breathing modes corresponding to the mixture of the high-symmetry stacking configurations and unaligned regions of monolayers. Only one breathing mode is observed outside the narrow range of twist angles. This indicates a stacking transition to unaligned monolayers with mismatched atom registry without the in-plane restoring force required to generate a shear mode. As a result, the variable interlayer coupling and spacing in transition metal dichalcogenide bilayers revealed in this study may provide a new platform for optoelectronic applications of these materials.« less

Ultrafast wavelength multiplexed broad bandwidth digital diffuse optical spectroscopy for in vivo extraction of tissue optical properties

NASA Astrophysics Data System (ADS)

Torjesen, Alyssa; Istfan, Raeef; Roblyer, Darren

2017-03-01

Frequency-domain diffuse optical spectroscopy (FD-DOS) utilizes intensity-modulated light to characterize optical scattering and absorption in thick tissue. Previous FD-DOS systems have been limited by large device footprints, complex electronics, high costs, and limited acquisition speeds, all of which complicate access to patients in the clinical setting. We have developed a new digital DOS (dDOS) system, which is relatively compact and inexpensive, allowing for simplified clinical use, while providing unprecedented measurement speeds. The dDOS system utilizes hardware-integrated custom board-level direct digital synthesizers and an analog-to-digital converter to generate frequency sweeps and directly measure signals utilizing undersampling at six wavelengths modulated at discrete frequencies from 50 to 400 MHz. Wavelength multiplexing is utilized to achieve broadband frequency sweep measurements acquired at over 97 Hz. When compared to a gold-standard DOS system, the accuracy of optical properties recovered with the dDOS system was within 5.3% and 5.5% for absorption and reduced scattering coefficient extractions, respectively. When tested in vivo, the dDOS system was able to detect physiological changes throughout the cardiac cycle. The new FD-dDOS system is fast, inexpensive, and compact without compromising measurement quality.

Artificial neural networks for retrieving absorption and reduced scattering spectra from frequency-domain diffuse reflectance spectroscopy at short source-detector separation

PubMed Central

Chen, Yu-Wen; Chen, Chien-Chih; Huang, Po-Jung; Tseng, Sheng-Hao

2016-01-01

Diffuse reflectance spectroscopy (DRS) based on the frequency-domain (FD) technique has been employed to investigate the optical properties of deep tissues such as breast and brain using source to detector separation up to 40 mm. Due to the modeling and system limitations, efficient and precise determination of turbid sample optical properties from the FD diffuse reflectance acquired at a source-detector separation (SDS) of around 1 mm has not been demonstrated. In this study, we revealed that at SDS of 1 mm, acquiring FD diffuse reflectance at multiple frequencies is necessary for alleviating the influence of inevitable measurement uncertainty on the optical property recovery accuracy. Furthermore, we developed artificial neural networks (ANNs) trained by Monte Carlo simulation generated databases that were capable of efficiently determining FD reflectance at multiple frequencies. The ANNs could work in conjunction with a least-square optimization algorithm to rapidly (within 1 second), accurately (within 10%) quantify the sample optical properties from FD reflectance measured at SDS of 1 mm. In addition, we demonstrated that incorporating the steady-state apparatus into the FD DRS system with 1 mm SDS would enable obtaining broadband absorption and reduced scattering spectra of turbid samples in the wavelength range from 650 to 1000 nm. PMID:27446671

Frequency-comb-assisted precision laser spectroscopy of CHF{sub 3} around 8.6 μm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gambetta, Alessio; Coluccelli, Nicola; Cassinerio, Marco

2015-12-21

We report a high-precision spectroscopic study of room-temperature trifluoromethane around 8.6 μm, using a CW quantum cascade laser phase-locked to a mid-infrared optical frequency comb. This latter is generated by a nonlinear down-conversion process starting from a dual-branch Er:fiber laser and is stabilized against a GPS-disciplined rubidium clock. By tuning the comb repetition frequency, several transitions falling in the υ{sub 5} vibrational band are recorded with a frequency resolution of 20 kHz. Due to the very dense spectra, a special multiple-line fitting code, involving a Voigt profile, is developed for data analysis. The combination of the adopted experimental approach andmore » survey procedure leads to fractional accuracy levels in the determination of line center frequencies, down to 2 × 10{sup −10}. Line intensity factors, pressure broadening, and shifting parameters are also provided.« less

Frequency-domain nonlinear regression algorithm for spectral analysis of broadband SFG spectroscopy.

PubMed

He, Yuhan; Wang, Ying; Wang, Jingjing; Guo, Wei; Wang, Zhaohui

2016-03-01

The resonant spectral bands of the broadband sum frequency generation (BB-SFG) spectra are often distorted by the nonresonant portion and the lineshapes of the laser pulses. Frequency domain nonlinear regression (FDNLR) algorithm was proposed to retrieve the first-order polarization induced by the infrared pulse and to improve the analysis of SFG spectra through simultaneous fitting of a series of time-resolved BB-SFG spectra. The principle of FDNLR was presented, and the validity and reliability were tested by the analysis of the virtual and measured SFG spectra. The relative phase, dephasing time, and lineshapes of the resonant vibrational SFG bands can be retrieved without any preset assumptions about the SFG bands and the incident laser pulses.

A new pulse width reduction technique for pulsed electron paramagnetic resonance spectroscopy.

PubMed

Ohba, Yasunori; Nakazawa, Shigeaki; Kazama, Shunji; Mizuta, Yukio

2008-03-01

We present a new technique for a microwave pulse modulator that generates a short microwave pulse of approximately 1ns for use in an electron paramagnetic resonance (EPR) spectrometer. A quadruple-frequency multiplier that generates a signal of 16-20GHz from an input of 4-5GHz was employed to reduce the rise and fall times of the pulse prepared by a PIN diode switch. We examined the transient response characteristics of a commercial frequency multiplier and found that the device can function as a multiplier for pulsed signal even though it was designed for continuous wave operation. We applied the technique to a Ku band pulsed EPR spectrometer and successfully observed a spin echo signal with a broad excitation bandwidth of approximately 1.6mT using 80 degrees pulses of 1.5ns.

High-power continuous-wave mid-infrared radiation generated by difference frequency mixing of diode-laser-seeded fiber amplifiers and its application to dual-beam spectroscopy

NASA Technical Reports Server (NTRS)

Lancaster, D. G.; Richter, D.; Curl, R. F.; Tittel, F. K.; Goldberg, L.; Koplow, J.

1999-01-01

We report the generation of up to 0.7 mW of narrow-linewidth (<60-MHz) radiation at 3.3 micrometers by difference frequency mixing of a Nd:YAG-seeded 1.6-W Yb fiber amplifier and a 1.5-micrometers diode-laser-seeded 0.6-W Er/Yb fiber amplifier in periodically poled LiNbO3. A conversion efficiency of 0.09%/W (0.47 mWW-2 cm-1) was achieved. A room-air CH4 spectrum acquired with a compact 80-m multipass cell and a dual-beam spectroscopic configuration indicates an absorption sensitivity of +/-2.8 x 10(-5) (+/-1 sigma), corresponding to a sub-parts-in-10(9) (ppb) CH4 sensitivity (0.8 ppb).

Frequency-Agile Differential Cavity Ring-Down Spectroscopy

NASA Astrophysics Data System (ADS)

Reed, Zachary; Hodges, Joseph

2015-06-01

The ultimate precision of highly sensitive cavity-enhanced spectroscopic measurements is often limited by interferences (etalons) caused by weak coupled-cavity effects. Differential measurements of ring-down decay constants have previously been demonstrated to largely cancel these effects, but the measurement acquisition rates were relatively low [1,2]. We have previously demonstrated the use of frequency agile rapid scanning cavity ring-down spectroscopy (FARS-CRDS) for acquisition of absorption spectra [3]. Here, the method of rapidly scanned, frequency-agile differential cavity ring-down spectroscopy (FADS-CRDS) is presented for reducing the effect of these interferences and other shot-to-shot statistical variations in measured decay times. To this end, an electro-optic phase modulator (EOM) with a bandwidth of 20 GHz is driven by a microwave source, generating pairs of sidebands on the probe laser. The optical resonator acts as a highly selective optical filter to all laser frequencies except for one tunable sideband. This sideband may be stepped arbitrarily from mode-to-mode of the ring-down cavity, at a rate limited only by the cavity buildup/decay time. The ability to probe any cavity mode across the EOM bandwidth enables a variety of methods for generating differential spectra. The differential mode spacing may be changed, and the effect of this method on suppressing the various coupled-cavity interactions present in the system is discussed. Alternatively, each mode may also be differentially referenced to a single point, providing immunity to temporal variations in the base losses of the cavity while allowing for conventional spectral fitting approaches. Differential measurements of absorption are acquired at 3.3 kHz and a minimum detectable absorption coefficient of 5 x10-12 cm-1 in 1 s averaging time is achieved. 1. J. Courtois, K. Bielska, and J.T Hodges J. Opt. Soc. Am. B, 30, 1486-1495, 2013 2. H.F. Huang and K.K. Lehmann App. Optics 49, 1378-1387, 2010 3. G.-W. Truong, K.O. Douglass, S.E. Maxwell, R.D. van Zee, D.F. Plusquellic, J.T. Hodges, and D.A. Long Nature Photonics, 7, 532-534, 2013

System for generating pluralities of optical pulses with predetermined frequencies in a temporally and spatially overlapped relationship

DOEpatents

Meyerhofer, David D.; Schmid, Ansgar W.; Chuang, Yung-ho

1992-01-01

Ultra short (pico second and shorter) laser pulses having components of different frequency which are overlapped coherently in space and with a predetermined constant relationship in time, are generated and may be used in applications where plural spectrally separate, time-synchronized pulses are needed as in wave-length resolved spectroscopy and spectral pump probe measurements for characterization of materials. A Chirped Pulse Amplifier (CPA), such as a regenerative amplifier, which provides amplified, high intensity pulses at the output thereof which have the same spatial intensity profile, is used to process a series of chirped pulses, each with a different central frequency (the desired frequencies contained in the output pulses). Each series of chirped pulses is obtained from a single chirped pulse by spectral windowing with a mask in a dispersive expansion stage ahead of the laser amplifier. The laser amplifier amplifies the pulses and provides output pulses with like spatial and temporal profiles. A compression stage then compresses the amplified pulses. All the individual pulses of different frequency, which originated in each single chirped pulse, are compressed and thereby coherently overlapped in space and time. The compressed pulses may be used for the foregoing purposes and other purposes wherien pulses having a plurality of discrete frequency components are required.

System for generating pluralities of optical pulses with predetermined frequencies in a temporally and spatially overlapped relationship

DOEpatents

Meyerhofer, D.D.; Schmid, A.W.; Chuang, Y.

1992-03-10

Ultrashort (pico second and shorter) laser pulses having components of different frequency which are overlapped coherently in space and with a predetermined constant relationship in time, are generated and may be used in applications where plural spectrally separate, time-synchronized pulses are needed as in wave-length resolved spectroscopy and spectral pump probe measurements for characterization of materials. A Chirped Pulse Amplifier (CPA), such as a regenerative amplifier, which provides amplified, high intensity pulses at the output thereof which have the same spatial intensity profile, is used to process a series of chirped pulses, each with a different central frequency (the desired frequencies contained in the output pulses). Each series of chirped pulses is obtained from a single chirped pulse by spectral windowing with a mask in a dispersive expansion stage ahead of the laser amplifier. The laser amplifier amplifies the pulses and provides output pulses with like spatial and temporal profiles. A compression stage then compresses the amplified pulses. All the individual pulses of different frequency, which originated in each single chirped pulse, are compressed and thereby coherently overlapped in space and time. The compressed pulses may be used for the foregoing purposes and other purposes wherien pulses having a plurality of discrete frequency components are required. 4 figs.

Theoretical extension and experimental demonstration of spectral compression in second-harmonic generation by Fresnel-inspired binary phase shaping

NASA Astrophysics Data System (ADS)

Li, Baihong; Dong, Ruifang; Zhou, Conghua; Xiang, Xiao; Li, Yongfang; Zhang, Shougang

2018-05-01

Selective two-photon microscopy and high-precision nonlinear spectroscopy rely on efficient spectral compression at the desired frequency. Previously, a Fresnel-inspired binary phase shaping (FIBPS) method was theoretically proposed for spectral compression of two-photon absorption and second-harmonic generation (SHG) with a square-chirped pulse. Here, we theoretically show that the FIBPS can introduce a negative quadratic frequency phase (negative chirp) by analogy with the spatial-domain phase function of Fresnel zone plate. Thus, the previous theoretical model can be extended to the case where the pulse can be transformed limited and in any symmetrical spectral shape. As an example, we experimentally demonstrate spectral compression in SHG by FIBPS for a Gaussian transform-limited pulse and show good agreement with the theory. Given the fundamental pulse bandwidth, a narrower SHG bandwidth with relatively high intensity can be obtained by simply increasing the number of binary phases. The experimental results also verify that our method is superior to that proposed in [Phys. Rev. A 46, 2749 (1992), 10.1103/PhysRevA.46.2749]. This method will significantly facilitate the applications of selective two-photon microscopy and spectroscopy. Moreover, as it can introduce negative dispersion, hence it can also be generalized to other applications in the field of dispersion compensation.

New Insights from Sum Frequency Generation Vibrational Spectroscopy into the Interactions of Islet Amyloid Polypeptides with Lipid Membranes

PubMed Central

Wang, Zhuguang; Batista, Victor S.; Yan, Elsa C. Y.

2016-01-01

Studies of amyloid polypeptides on membrane surfaces have gained increasing attention in recent years. Several studies have revealed that membranes can catalyze protein aggregation and that the early products of amyloid aggregation can disrupt membrane integrity, increasing water permeability and inducing ion cytotoxicity. Nonetheless, probing aggregation of amyloid proteins on membrane surfaces is challenging. Surface-specific methods are required to discriminate contributions of aggregates at the membrane interface from those in the bulk phase and to characterize protein secondary structures in situ and in real time without the use of perturbing spectroscopic labels. Here, we review the most recent applications of sum frequency generation (SFG) vibrational spectroscopy applied in conjunction with computational modeling techniques, a joint experimental and computational methodology that has provided valuable insights into the aggregation of islet amyloid polypeptide (IAPP) on membrane surfaces. These applications show that SFG can provide detailed information about structures, kinetics, and orientation of IAPP during interfacial aggregation, relevant to the molecular mechanisms of type II diabetes. These recent advances demonstrate the promise of SFG as a new approach for studying amyloid diseases at the molecular level and for the rational drug design targeting early aggregation products on membrane surfaces. PMID:26697504

Tailoring the transverse mode of a high-finesse optical resonator with stepped mirrors

NASA Astrophysics Data System (ADS)

Högner, M.; Saule, T.; Lilienfein, N.; Pervak, V.; Pupeza, I.

2018-02-01

Enhancement cavities (ECs) seeded with femtosecond pulses have developed into the most powerful technique for high-order harmonic generation (HHG) at repetition rates in the tens of MHz. Here, we demonstrate the feasibility of controlling the phase front of the excited transverse eigenmode of a ring EC by using mirrors with stepped surface profiles, while maintaining the high finesse required to reach the peak intensities necessary for HHG. The two lobes of a {{TEM}}01 mode of a 3.93 m long EC, seeded with a single-frequency laser, are delayed by 15.6 fs with respect to each other before a tight focus, and the delay is reversed after the focus. The tailored transverse mode exhibits an on-axis intensity maximum in the focus. Furthermore, the geometry is designed to generate a rotating wavefront in the focus when few-cycle pulses circulate in the EC. This paves the way to gating isolated attosecond pulses (IAPs) in a transverse manner (similarly to the attosecond lighthouse), heralding IAPs at repetition rates well into the multi-10 MHz range. In addition, these results promise high-efficiency harmonic output coupling from ECs in general, with an unparalleled power scalability. These prospects are expected to tremendously benefit photoelectron spectroscopy and extreme-ultraviolet frequency comb spectroscopy.

Theoretical vibrational sum-frequency generation spectroscopy of water near lipid and surfactant monolayer interfaces.

PubMed

Roy, S; Gruenbaum, S M; Skinner, J L

2014-11-14

Understanding the structure of water near cell membranes is crucial for characterizing water-mediated events such as molecular transport. To obtain structural information of water near a membrane, it is useful to have a surface-selective technique that can probe only interfacial water molecules. One such technique is vibrational sum-frequency generation (VSFG) spectroscopy. As model systems for studying membrane headgroup/water interactions, in this paper we consider lipid and surfactant monolayers on water. We adopt a theoretical approach combining molecular dynamics simulations and phase-sensitive VSFG to investigate water structure near these interfaces. Our simulated spectra are in qualitative agreement with experiments and reveal orientational ordering of interfacial water molecules near cationic, anionic, and zwitterionic interfaces. OH bonds of water molecules point toward an anionic interface leading to a positive VSFG peak, whereas the water hydrogen atoms point away from a cationic interface leading to a negative VSFG peak. Coexistence of these two interfacial water species is observed near interfaces between water and mixtures of cationic and anionic lipids, as indicated by the presence of both negative and positive peaks in their VSFG spectra. In the case of a zwitterionic interface, OH orientation is toward the interface on the average, resulting in a positive VSFG peak.

Sandwich Panels Evaluated With Ultrasonic Spectroscopy

NASA Technical Reports Server (NTRS)

Cosgriff, Laura M.

2004-01-01

Enhanced, lightweight material systems, such as 17-4PH stainless steel sandwich panels are being developed for use as fan blades and fan containment systems for next-generation engines. The bond strength between the core and face sheets is critical in maintaining the structural integrity of the sandwich structure. To improve the inspection and production of these systems, researchers at the NASA Glenn Research Center are using nondestructive evaluation (NDE) techniques, such as ultrasonic spectroscopy, to evaluate the brazing quality between the face plates and the metallic foam core. The capabilities and limitations of a swept-frequency approach to ultrasonic spectroscopy were evaluated with respect to these sandwich structures. This report discusses results from three regions of a sandwich panel representing different levels of brazing quality between the outer face plates and a metallic foam core. Each region was investigated with ultrasonic spectroscopy. Then, on the basis of the NDE results, three shear specimens sectioned from the sandwich panel to contain each of these regions were mechanically tested.

Dielectric Properties of Generation 3 Pamam Dendrimer Nanocomposites

NASA Astrophysics Data System (ADS)

Ristić, Sanja; Mijović, Jovan

2008-08-01

Broadband dielectric relaxation spectroscopy (DRS) was employed to study molecular dynamics of blends composed of generation 3 poly(amidoamine) (PAMAM) dendrimers with ethylenediamine core and amino surface groups and four linear polymers: poly(propylene oxide)—PPO, two block copolymers, poly(propylene oxide)/poly(ethylene oxide)—PPO/PEO with different mol ratios (29/6 and 10/31) and poly(ethylene oxide)—PEO. The results were generated over a broad range of frequency. Dielectric spectra of dendrimers in PPO matrix reveal slight shift of normal and segmental processes to higher frequency with increasing concentration of dendrimers. In the 29PPO/6PEO matrix, no effect of concentration on the average relaxation time for normal and segmental processes was observed. In the 10PPO/31PEO matrix the relaxation time of the segmental process increases with increasing dendrimer concentration, while in the PEO matrix, local processes in dendrimers slow down. A detailed analysis of the effect of concentration of dendrimers and morphology of polymer matrix on the dielectric properties of dendrimer nanocomposites will be presented.

Band excitation method applicable to scanning probe microscopy

DOEpatents

Jesse, Stephen [Knoxville, TN; Kalinin, Sergei V [Knoxville, TN

2010-08-17

Methods and apparatus are described for scanning probe microscopy. A method includes generating a band excitation (BE) signal having finite and predefined amplitude and phase spectrum in at least a first predefined frequency band; exciting a probe using the band excitation signal; obtaining data by measuring a response of the probe in at least a second predefined frequency band; and extracting at least one relevant dynamic parameter of the response of the probe in a predefined range including analyzing the obtained data. The BE signal can be synthesized prior to imaging (static band excitation), or adjusted at each pixel or spectroscopy step to accommodate changes in sample properties (adaptive band excitation). An apparatus includes a band excitation signal generator; a probe coupled to the band excitation signal generator; a detector coupled to the probe; and a relevant dynamic parameter extractor component coupled to the detector, the relevant dynamic parameter extractor including a processor that performs a mathematical transform selected from the group consisting of an integral transform and a discrete transform.

Band excitation method applicable to scanning probe microscopy

DOEpatents

Jesse, Stephen; Kalinin, Sergei V

2013-05-28

Methods and apparatus are described for scanning probe microscopy. A method includes generating a band excitation (BE) signal having finite and predefined amplitude and phase spectrum in at least a first predefined frequency band; exciting a probe using the band excitation signal; obtaining data by measuring a response of the probe in at least a second predefined frequency band; and extracting at least one relevant dynamic parameter of the response of the probe in a predefined range including analyzing the obtained data. The BE signal can be synthesized prior to imaging (static band excitation), or adjusted at each pixel or spectroscopy step to accommodate changes in sample properties (adaptive band excitation). An apparatus includes a band excitation signal generator; a probe coupled to the band excitation signal generator; a detector coupled to the probe; and a relevant dynamic parameter extractor component coupled to the detector, the relevant dynamic parameter extractor including a processor that performs a mathematical transform selected from the group consisting of an integral transform and a discrete transform.

Infrared Spectroscopy on Smoke Produced by Cauterization of Animal Tissue

PubMed Central

Gianella, Michele; Sigrist, Markus W.

2010-01-01

In view of in vivo surgical smoke studies a difference-frequency-generation (DFG) laser spectrometer (spectral range 2900–3144 cm−1) and a Fourier-transform infrared (FTIR) spectrometer were employed for infrared absorption spectroscopy. The chemical composition of smoke produced in vitro with an electroknife by cauterization of different animal tissues in different atmospheres was investigated. Average concentrations derived are: water vapor (0.87%), methane (20 ppm), ethane (4.8 ppm), ethene (17 ppm), carbon monoxide (190 ppm), nitric oxide (25 ppm), nitrous oxide (40 ppm), ethyne (50 ppm) and hydrogen cyanide (25 ppm). No correlation between smoke composition and the atmosphere or the kind of cauterized tissue was found. PMID:22319267

Coherent Two-Dimensional Terahertz Magnetic Resonance Spectroscopy of Collective Spin Waves.

PubMed

Lu, Jian; Li, Xian; Hwang, Harold Y; Ofori-Okai, Benjamin K; Kurihara, Takayuki; Suemoto, Tohru; Nelson, Keith A

2017-05-19

We report a demonstration of two-dimensional (2D) terahertz (THz) magnetic resonance spectroscopy using the magnetic fields of two time-delayed THz pulses. We apply the methodology to directly reveal the nonlinear responses of collective spin waves (magnons) in a canted antiferromagnetic crystal. The 2D THz spectra show all of the third-order nonlinear magnon signals including magnon spin echoes, and 2-quantum signals that reveal pairwise correlations between magnons at the Brillouin zone center. We also observe second-order nonlinear magnon signals showing resonance-enhanced second-harmonic and difference-frequency generation. Numerical simulations of the spin dynamics reproduce all of the spectral features in excellent agreement with the experimental 2D THz spectra.

Nanocylindrical confinement imparts highest structural order in molecular self-assembly of organophosphonates on aluminum oxide.

PubMed

Pathak, Anshuma; Bora, Achyut; Braunschweig, Björn; Meltzer, Christian; Yan, Hongdan; Lemmens, Peter; Daum, Winfried; Schwartz, Jeffrey; Tornow, Marc

2017-05-18

We report the impact of geometrical constraint on intramolecular interactions in self-assembled monolayers (SAMs) of alkylphosphonates grown on anodically oxidized aluminum (AAO). Molecular order in these films was determined by sum frequency generation (SFG) spectroscopy, a more sensitive measure of order than infrared absorption spectroscopy. Using SFG we show that films grown on AAO are, within detection limits, nearly perfectly ordered in an all-trans alkyl chain configuration. In marked contrast, films formed on planar, plasma-oxidized aluminum oxide or α-Al 2 O 3 (0001) are replete with gauche defects. We attribute these differences to the nanocylindrical structure of AAO, which enforces molecular confinement.

Metallic cyanoacetylides of copper, silver and gold: generation and structural characterization.

PubMed

Cabezas, Carlos; Barrientos, Carmen; Largo, Antonio; Guillemin, Jean-Claude; Alonso, J L

2016-10-19

The metallic cyanoacetylides CuCCCN, AgCCCN, and AuCCCN have been synthesized in the throat of a pulsed supersonic expansion by reaction of metal vapors, produced by laser ablation, and BrCCCN. Their pure rotational spectra in the (X 1 Σ + ) electronic ground state were observed by Fourier transform microwave spectroscopy in the 2-10 GHz frequency region. Importantly, the rotational spectroscopy constants determined from the analysis of the rotational spectra clearly established the existence of metal-CCCN arrangements for all the mentioned cyanoacetylides. A study of the chemical bonding by means of a topological analysis of the electron density helps to understand the preference for metal-C bonding over metal-N bonding.

A 10 micron laser heterodyne spectrometer for remote detection of trace gases

NASA Technical Reports Server (NTRS)

Mumma, M. J.; Kostiuk, T.; Buhl, D.

1978-01-01

Infrared heterodyne spectroscopy provides a means of measuring the intensity profiles of individual rotation-vibration spectral lines with high sensitivity. Considerable effort has been expended on optimizing these instruments for remote measurements of gases in planetary atmospheres with the result that present-generation spectrometers are beginning to provide new and startling results on the planets. The fundamental principles of laser heterodyne spectroscopy are discussed. Detailed considerations of the optical design and the electronic design of the spectral-line receiver are given. Representative results obtained with this spectrometer are discussed, including precision frequency measurements of NH3 (nu-2) lines, detection of auroral emission from Jupiter, and measurements of terrestrial O3 and CO2.

Temporally resolved diagnosis of an atmospheric-pressure pulse-modulated argon surface wave plasma by optical emission spectroscopy

NASA Astrophysics Data System (ADS)

Chen, Chuan-Jie; Li, Shou-Zhe; Zhang, Jialiang; Liu, Dongping

2018-01-01

A pulse-modulated argon surface wave plasma generated at atmospheric pressure is characterized by means of temporally resolved optical emission spectroscopy (OES). The temporal evolution of the gas temperature, the electron temperature and density, the radiative species of atomic Ar, and the molecular band of OH(A) and N2(C) are investigated experimentally by altering the instantaneous power, pulse repetitive frequency, and duty ratio. We focused on the physical phenomena occurring at the onset of the time-on period and after the power interruption at the start of the time-off period. Meanwhile, the results are discussed qualitatively for an in-depth insight of its dynamic evolution.

Nonlinear silicon photonics

NASA Astrophysics Data System (ADS)

Borghi, M.; Castellan, C.; Signorini, S.; Trenti, A.; Pavesi, L.

2017-09-01

Silicon photonics is a technology based on fabricating integrated optical circuits by using the same paradigms as the dominant electronics industry. After twenty years of fervid development, silicon photonics is entering the market with low cost, high performance and mass-manufacturable optical devices. Until now, most silicon photonic devices have been based on linear optical effects, despite the many phenomenologies associated with nonlinear optics in both bulk materials and integrated waveguides. Silicon and silicon-based materials have strong optical nonlinearities which are enhanced in integrated devices by the small cross-section of the high-index contrast silicon waveguides or photonic crystals. Here the photons are made to strongly interact with the medium where they propagate. This is the central argument of nonlinear silicon photonics. It is the aim of this review to describe the state-of-the-art in the field. Starting from the basic nonlinearities in a silicon waveguide or in optical resonator geometries, many phenomena and applications are described—including frequency generation, frequency conversion, frequency-comb generation, supercontinuum generation, soliton formation, temporal imaging and time lensing, Raman lasing, and comb spectroscopy. Emerging quantum photonics applications, such as entangled photon sources, heralded single-photon sources and integrated quantum photonic circuits are also addressed at the end of this review.

Compact Tunable Narrowband Terahertz-Wave Source Based on Difference Frequency Generation Pumped by Dual Fiber Lasers in MgO:LiNbO3

NASA Astrophysics Data System (ADS)

Wada, Yoshio; Satoh, Takumi; Higashi, Yasuhiro; Urata, Yoshiharu

2017-12-01

We demonstrate a high-average-power, single longitudinal-mode, and tunable terahertz (THz)-wave source based on difference frequency generation (DFG) in a MgO:LiNbO3 (MgO:LN) crystal. The waves for DFG are generated using a pair of Yb-doped pulsed fiber lasers with a master oscillator power fiber amplifier configuration. The average power of the THz-wave output reaches 450 μW at 1.07 THz (280 μm) at a linewidth of 7.2 GHz, and the tunability ranges from 0.35 to 1.07 THz under the pulse repetition frequency of 500 kHz. A short burn-in test of the THz wave is also carried out, and the output power stability is within ± 5% of the averaged power without any active stabilizing technique. The combination of MgO:LN-DFG and stable and robust fiber laser sources is highly promising for the development of high-average-power THz-wave sources, particularly in the high transmission sub-THz region. This approach may enable new applications of THz-wave spectroscopy in imaging and remote sensing.

An innovative Yb-based ultrafast deep ultraviolet source for time-resolved photoemission experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boschini, F.; Hedayat, H.; Dallera, C.

2014-12-15

Time- and angle-resolved photoemission spectroscopy is a powerful technique to study ultrafast electronic dynamics in solids. Here, an innovative optical setup based on a 100-kHz Yb laser source is presented. Exploiting non-collinear optical parametric amplification and sum-frequency generation, ultrashort pump (hν = 1.82 eV) and ultraviolet probe (hν = 6.05 eV) pulses are generated. Overall temporal and instrumental energy resolutions of, respectively, 85 fs and 50 meV are obtained. Time- and angle-resolved measurements on BiTeI semiconductor are presented to show the capabilities of the setup.

A simplified scheme for generating narrow-band mid-ultraviolet laser radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Almog, G.; Ludwig-Maximilians-Universität, Geschwister-Scholl-Platz 1, 80539 München; Scholz, M., E-mail: Matthias.Scholz@toptica.com

2015-03-15

We report on the development and characterization of continuous, narrow-band, and tunable laser systems that use direct second-harmonic generation from blue and green diode lasers with an output power level of up to 11.1 mW in the mid-ultraviolet. One of our laser systems was tuned to the mercury 6{sup 1}S{sub 0} → 6{sup 3}P{sub 1} intercombination line at 253.7 nm. We could perform Doppler-free saturation spectroscopy on this line and were able to lock our laser to the transition frequency on long time scales.

Near-IR laser frequency standard stabilized using FM-spectroscopy

NASA Astrophysics Data System (ADS)

Ružička, Bohdan; Číp, Ondřej; Lazar, Josef

2006-02-01

At the present time fiber-optics and optical communication are in rapid progress. Modern technologies such as DWDM (Dense Wavelength Division Multiplex) need precise stability of laser frequencies. According to this fact, requirements of new etalons of optical frequencies in the telecommunication band is rapidly growing. Lasers working in near infrared telecommunication band (1500-1600 nm) can be stabilized to 12C IIH II or 13C IIH II (acetylene) gas absorption lines. The acetylene gas absorption has been widely studied and accepted by international bodies of standardization as a primary wavelength reference in the near infrared band around 1550nm. Our aim was to design and develop a compact fibre optics laser system generating coherent light in near-JR band with high frequency stability (at least 1.10 -8). This system should become a base for realization of a primary frequency standard for optical communications in the Czech Republic. Such an etalon will be needed for calibration of wavelength-meters and spectral analysers for DWDM communication systems. We are co-operating with CMI (Czech Metrology Institute) on this project. We present stabilized laser system based on a single frequency DFB (Distributed Feedback) laser diode with a narrow spectral profile. The laser is pre-stabilized by means of the FM-spectroscopy on a passive resonator. Thanks to a fast feed-back loop we are able to improve spectral characteristics of the laser. The laser frequency is locked by a relatively slow second feed-back loop on an absorption line of acetylene vapour which is sealed in a cell under the optimised pressure.

Remotely Exploring Deeper-Into-Matter by Non-Contact Detection of Audible Transients Excited by Laser Radiation

PubMed Central

Moros, Javier; Gaona, Inmaculada; Laserna, J. Javier

2017-01-01

An acoustic spectroscopic approach to detect contents within different packaging, with substantially wider applicability than other currently available subsurface spectroscopies, is presented. A frequency-doubled Nd:YAG (neodymium-doped yttrium aluminum garnet) pulsed laser (13 ns pulse length) operated at 1 Hz was used to generate the sound field of a two-component system at a distance of 50 cm. The acoustic emission was captured using a unidirectional microphone and analyzed in the frequency domain. The focused laser pulse hitting the system, with intensity above that necessary to ablate the irradiated surface, transferred an impulsive force which led the structure to vibrate. Acoustic airborne transients were directly radiated by the vibrating elastic structure of the outer component that excited the surrounding air in contact with. However, under boundary conditions, sound field is modulated by the inner component that modified the dynamical integrity of the system. Thus, the resulting frequency spectra are useful indicators of the concealed content that influences the contributions originating from the wall of the container. High-quality acoustic spectra could be recorded from a gas (air), liquid (water), and solid (sand) placed inside opaque chemical-resistant polypropylene and stainless steel sample containers. Discussion about effects of laser excitation energy and sampling position on the acoustic emission events is reported. Acoustic spectroscopy may complement the other subsurface alternative spectroscopies, severely limited by their inherent optical requirements for numerous detection scenarios. PMID:29261126

Gigahertz dual-comb modelocked diode-pumped semiconductor and solid-state lasers

NASA Astrophysics Data System (ADS)

Link, S. M.; Mangold, M.; Golling, M.; Klenner, A.; Keller, U.

2016-03-01

We present a simple approach to generate simultaneously two gigahertz mode-locked pulse trains from a single gain element. A bi-refringent crystal in the laser cavity splits the one cavity beam into two cross-polarized and spatially separated beams. This polarization-duplexing is successfully demonstrated for both a semiconductor disk laser (i.e. MIXSEL) and a diode-pumped solid-state Nd:YAG laser. The beat between the two beams results in a microwave frequency comb, which represents a direct link between the terahertz optical frequencies and the electronically accessible microwave regime. This dual-output technique enables compact and cost-efficient dual-comb lasers for spectroscopy applications.

Frequency comb transferred by surface plasmon resonance

PubMed Central

Geng, Xiao Tao; Chun, Byung Jae; Seo, Ji Hoon; Seo, Kwanyong; Yoon, Hana; Kim, Dong-Eon; Kim, Young-Jin; Kim, Seungchul

2016-01-01

Frequency combs, millions of narrow-linewidth optical modes referenced to an atomic clock, have shown remarkable potential in time/frequency metrology, atomic/molecular spectroscopy and precision LIDARs. Applications have extended to coherent nonlinear Raman spectroscopy of molecules and quantum metrology for entangled atomic qubits. Frequency combs will create novel possibilities in nano-photonics and plasmonics; however, its interrelation with surface plasmons is unexplored despite the important role that plasmonics plays in nonlinear spectroscopy and quantum optics through the manipulation of light on a subwavelength scale. Here, we demonstrate that a frequency comb can be transformed to a plasmonic comb in plasmonic nanostructures and reverted to the original frequency comb without noticeable degradation of <6.51 × 10−19 in absolute position, 2.92 × 10−19 in stability and 1 Hz in linewidth. The results indicate that the superior performance of a well-defined frequency comb can be applied to nanoplasmonic spectroscopy, quantum metrology and subwavelength photonic circuits. PMID:26898307

Frequency stabilization of a 1083 nm fiber laser to {sup 4}He transition lines with optical heterodyne saturation spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, W.; Peng, X., E-mail: xiangpeng@pku.edu.cn; Li, W.

2014-07-15

Two kinds of optical heterodyne saturation spectroscopies, namely, frequency modulation spectroscopy (FMS) and modulation transfer spectroscopy (MTS), are demonstrated for locking a fiber laser to the transition lines of metastable {sup 4}He atoms around 1083 nm. The servo-loop error signals of FMS and MTS for stabilizing laser frequency are optimized by studying the dependence of the peak-to-peak amplitude and slope on the optical power of pump and probe beams. A comparison of the stabilization performances of FMS/MTS and polarization spectroscopy (PS) is presented, which shows that MTS exhibits relatively superior performance with the least laser frequency fluctuation due to itsmore » flat-background dispersive signal, originated from the four-wave mixing process. The Allan deviation of the stabilized laser frequency is 5.4 × 10{sup −12}@100 s with MTS for data acquired in 1000 s, which is sufficiently applicable for fields like laser cooling, optical pumping, and optical magnetometry.« less

ULTRAFAST CHEMISTRY: Using Time-Resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics

NASA Astrophysics Data System (ADS)

Nibbering, Erik T. J.; Fidder, Henk; Pines, Ehud

2005-05-01

Time-resolved infrared (IR) and Raman spectroscopy elucidates molecular structure evolution during ultrafast chemical reactions. Following vibrational marker modes in real time provides direct insight into the structural dynamics, as is evidenced in studies on intramolecular hydrogen transfer, bimolecular proton transfer, electron transfer, hydrogen bonding during solvation dynamics, bond fission in organometallic compounds and heme proteins, cis-trans isomerization in retinal proteins, and transformations in photochromic switch pairs. Femtosecond IR spectroscopy monitors the site-specific interactions in hydrogen bonds. Conversion between excited electronic states can be followed for intramolecular electron transfer by inspection of the fingerprint IR- or Raman-active vibrations in conjunction with quantum chemical calculations. Excess internal vibrational energy, generated either by optical excitation or by internal conversion from the electronic excited state to the ground state, is observable through transient frequency shifts of IR-active vibrations and through nonequilibrium populations as deduced by Raman resonances.

SFG study of methanol dissociative adsorption at Pt(1 0 0), Pt(1 1 0) and Pt(1 1 1) electrodes surfaces

NASA Astrophysics Data System (ADS)

Vidal, F.; Busson, B.; Six, C.; Pluchery, O.; Tadjeddine, A.

2002-04-01

The Pt( hkl)/methanol in acidic solution interface which constitutes a model of the anodic part of a fuel cell is studied by infrared-visible sum frequency generation vibrational spectroscopy. Methanol dissociative adsorption leads to CO poisoning of the Pt electrode surfaces. The structure of the CO/Pt( hkl) interface depends strongly on the orientation of the surface electrode.

Ultrashort Pulse (USP) Laser-Matter Interactions

DTIC Science & Technology

2013-03-05

spectroscopy • Frequency/time transfer • High-capacity comms • Coherent LIDAR • Optical clocks • Calibration Material Science ultrashort, high...Laboratory 41 Laser -driven x-rays generation (0.1 – 10 MeV) • Scattering from a 300 MeV electron beam can Doppler shift a 1-eV energy laser ...1 Integrity  Service  Excellence Ultrashort Pulse (USP) Laser – Matter Interactions 5 MAR 2013 Dr. Riq Parra Program Officer AFOSR/RTB

Two-photon Direct Frequency Comb Spectroscopy of Alkali Atoms

NASA Astrophysics Data System (ADS)

Nguyen, Khoa; Pradhananga, Trinity; Palm, Christopher; Stalnaker, Jason; Kimball, Derek Jackson

2012-06-01

We are using direct frequency comb spectroscopy to study transition frequencies and excited state hyperfine structure in potassium and rubidium using 2-photon transitions excited directly with the frequency-doubled output of a erbium fiber optical frequency comb. The frequency comb output is directed in two counterpropagating directions through a vapor cell containing the atomic vapor of interest. A pair of optical filters is used to select teeth of the comb in order to identify the transition wavelengths. A photomultiplier tube (PMT) measures fluorescence from a decay channel wavelength selected with another optical filter. Using different combinations of filters enables a wide range of transitions to be investigated. By scanning the repetition rate, a Doppler-free spectrum can be obtained enabling kHz-resolution spectral measurements. The thermal motion of the atoms in the vapor cell actually eliminates the need to fine-tune the offset frequency and repetition rate, alleviating a somewhat challenging requirement for spectroscopy of cold atoms. Our investigations are laying the groundwork for a long-term research program to use direct frequency comb spectroscopy to understand the complex spectra of rare-earth atoms.

Direct Frequency Comb Spectroscopy of Alkali Atoms

NASA Astrophysics Data System (ADS)

Pradhananga, Trinity; Palm, Christopher; Nguyen, Khoa; Guttikonda, Srikanth; Kimball, Derek Jackson

2011-11-01

We are using direct frequency comb spectroscopy to study transition frequencies and excited state hyperfine structure in potassium and rubidium using 2-photon transitions excited directly with the frequency-doubled output of a erbium fiber optical frequency comb. The frequency comb output is directed in two counterpropagating directions through a vapor cell containing the atomic vapor of interest. A pair of optical filters is used to select teeth of the comb in order to identify the transition wavelengths. A photomultiplier tube (PMT) measures fluorescence from a decay channel wavelength selected with another optical filter. Using different combinations of filters enables a wide range of transitions to be investigated. By scanning the repetition rate, a Doppler-free spectrum can be obtained enabling kHz-resolution spectral measurements. The thermal motion of the atoms in the vapor cell actually eliminates the need to fine-tune the offset frequency and repetition rate, alleviating a somewhat challenging requirement for spectroscopy of cold atoms. Our investigations are laying the groundwork for a long-term research program to use direct frequency comb spectroscopy to understand the complex spectra of rare-earth atoms.

Quantum Mechanical Calculations of Vibrational Sum-Frequency-Generation (SFG) Spectra of Cellulose: Dependence of the CH and OH Peak Intensity on the Polarity of Cellulose Chains within the SFG Coherence Domain.

PubMed

Lee, Christopher M; Chen, Xing; Weiss, Philip A; Jensen, Lasse; Kim, Seong H

2017-01-05

Vibrational sum-frequency-generation (SFG) spectroscopy is capable of selectively detecting crystalline biopolymers interspersed in amorphous polymer matrices. However, the spectral interpretation is difficult due to the lack of knowledge on how spatial arrangements of crystalline segments influence SFG spectra features. Here we report time-dependent density functional theory (TD-DFT) calculations of cellulose crystallites in intimate contact with two different polarities: parallel versus antiparallel. TD-DFT calculations reveal that the CH/OH intensity ratio is very sensitive to the polarity of the crystallite packing. Theoretical calculations of hyperpolarizability tensors (β abc ) clearly show the dependence of SFG intensities on the polarity of crystallite packing within the SFG coherence length, which provides the basis for interpretation of the empirically observed SFG features of native cellulose in biological systems.

The harmonic state of quantum cascade lasers: origin, control, and prospective applications [Invited].

PubMed

Piccardo, Marco; Chevalier, Paul; Mansuripur, Tobias S; Kazakov, Dmitry; Wang, Yongrui; Rubin, Noah A; Meadowcroft, Lauren; Belyanin, Alexey; Capasso, Federico

2018-04-16

The recently discovered ability of the quantum cascade laser to produce a harmonic frequency comb has attracted new interest in these devices for both applications and fundamental laser physics. In this review we present an extensive experimental phenomenology of the harmonic state, including its appearance in mid-infrared and terahertz quantum cascade lasers, studies of its destabilization induced by delayed optical feedback, and the assessment of its frequency comb nature. A theoretical model explaining its origin as due to the mutual interaction of population gratings and population pulsations inside the laser cavity will be described. We explore different approaches to control the spacing of the harmonic state, such as optical injection seeding and variation of the device temperature. Prospective applications of the harmonic state include microwave and terahertz generation, picosecond pulse generation in the mid-infrared, and broadband spectroscopy.

Plasma characteristics of argon glow discharge produced by AC power supply operating at low frequencies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kongpiboolkid, Watcharapon; Mongkolnavin, Rattachat; Plasma Technology and Nuclear Fusion Research Unit, Chulalongkorn University, Bangkok

2015-04-24

Non-thermal properties of Argon glow discharge operating with various operating pressures were measured and presented in this work. The Argon plasma is produced by a parallel conducting electrodes coupling with a high voltage AC power supply. The power supply can generate high AC voltage at various frequencies. The frequencies for the operation are in the range of a few kHz. The system is capable of generating electric field between the two metal electrodes discharge system. The characteristics of plasma produced were measured by optical emission spectroscopy (OES) technique where electron temperature (T{sub e}) and electron number density (n{sub e}) canmore » be determined by line intensity ratio method. The value of electron number density was then determined from the Saha-Eggert equation. Our results show that the electron number density of the discharge obtained is of the order of 10{sup −17} − 10{sup −18} m{sup −3} where the electron temperature is between 1.00−2.00 eV for various operating frequencies used which are in good agreement with similar results published earlier.« less

Atmospheric-pressure diffuse dielectric barrier discharges in Ar/O2 gas mixture using 200 kHz/13.56 MHz dual frequency excitation

NASA Astrophysics Data System (ADS)

Liu, Y.; Starostin, S. A.; Peeters, F. J. J.; van de Sanden, M. C. M.; de Vries, H. W.

2018-03-01

Atmospheric-pressure diffuse dielectric barrier discharges (DBDs) were obtained in Ar/O2 gas mixture using dual-frequency (DF) excitation at 200 kHz low frequency (LF) and 13.56 MHz radio frequency (RF). The excitation dynamics and the plasma generation mechanism were studied by means of electrical characterization and phase resolved optical emission spectroscopy (PROES). The DF excitation results in a time-varying electric field which is determined by the total LF and RF gas voltage and the spatial ion distribution which only responds to the LF component. By tuning the amplitude ratio of the superimposed LF and RF signals, the effect of each frequency component on the DF discharge mechanism was analysed. The LF excitation results in a transient plasma with the formation of an electrode sheath and therefore a pronounced excitation near the substrate. The RF oscillation allows the electron trapping in the gas gap and helps to improve the plasma uniformity by contributing to the pre-ionization and by controlling the discharge development. The possibility of temporally modifying the electric field and thus the plasma generation mechanism in the DF discharge exhibits potential applications in plasma-assisted surface processing and plasma-assisted gas phase chemical conversion.

Hyper-Ramsey spectroscopy of optical clock transitions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yudin, V. I.; Taichenachev, A. V.; Oates, C. W.

2010-07-15

We present nonstandard optical Ramsey schemes that use pulses individually tailored in duration, phase, and frequency to cancel spurious frequency shifts related to the excitation itself. In particular, the field shifts and their uncertainties can be radically suppressed (by two to four orders of magnitude) in comparison with the usual Ramsey method (using two equal pulses) as well as with single-pulse Rabi spectroscopy. Atom interferometers and optical clocks based on two-photon transitions, heavily forbidden transitions, or magnetically induced spectroscopy could significantly benefit from this method. In the latter case, these frequency shifts can be suppressed considerably below a fractional levelmore » of 10{sup -17}. Moreover, our approach opens the door for high-precision optical clocks based on direct frequency comb spectroscopy.« less

Low-Cost, Single-Frequency Sources for Spectroscopy using Conventional Fabry-Perot Diode Lasers

NASA Technical Reports Server (NTRS)

Duerksen, Gary L.; Krainak, Michael A.

1999-01-01

Commercial (uncoated) Fabry-Perot laser diodes are converted to single-frequency spectroscopy sources by passively locking the laser frequency to the band edge of a fiber Bragg grating, which phase-locks the laser oscillations through self-injection seeding.

Low-Cost, Single-Frequency Sources for Spectroscopy Using Conventional Fabry-Perot Diode Lasers

NASA Technical Reports Server (NTRS)

Krainak, Michael A.; Duerksen, Gary L.

1999-01-01

Commercial (uncoated) Fabry-Perot laser diodes are converted to single-frequency spectroscopy sources by passively locking the laser frequency to the band edge of a fiber Bragg grating, which phase-locks the laser oscillations through self-injection seeding.

Terahertz photonic crystals

NASA Astrophysics Data System (ADS)

Jian, Zhongping

This thesis describes the study of two-dimensional photonic crystals slabs with terahertz time domain spectroscopy. In our study we first demonstrate the realization of planar photonic components to manipulate terahertz waves, and then characterize photonic crystals using terahertz pulses. Photonic crystal slabs at the scale of micrometers are first designed and fabricated free of defects. Terahertz time domain spectrometer generates and detects the electric fields of single-cycle terahertz pulses. By putting photonic crystals into waveguide geometry, we successfully demonstrate planar photonic components such as transmission filters, reflection frequency-selective filters, defects modes as well as superprisms. In the characterization study of out-of-plane properties of photonic crystal slabs, we observe very strong dispersion at low frequencies, guided resonance modes at middle frequencies, and a group velocity anomaly at high frequencies. We employ Finite Element Method and Finite-Difference Time-Domain method to simulate the photonic crystals, and excellent agreement is achieved between simulation results and experimental results.

Ultra-wideband electronics, design methods, algorithms, and systems for dielectric spectroscopy of isolated B16 tumor cells in liquid medium

NASA Astrophysics Data System (ADS)

Maxwell, Erick N.

Quantifying and characterizing isolated tumor cells (ITCs) is of interest in surgical pathology and cytology for its potential to provide data for cancer staging, classification, and treatment. Although the independent prognostic significance of circulating ITCs has not been proven, their presence is gaining clinical relevance as an indicator. However, researchers have not established an optimal method for detecting ITCs. Consequently, this Ph.D. dissertation is concerned with the development and evaluation of dielectric spectroscopy as a low-cost method for cell characterization and quantification. In support of this goal, ultra-wideband (UWB), microwave pulse generator circuits, coaxial transmission line fixtures, permittivity extraction algorithms, and dielectric spectroscopy measurement systems were developed for evaluating the capacity to quantify B16-F10 tumor cells in suspension. First, this research addressed challenges in developing tunable UWB circuits for pulse generation. In time-domain dielectric spectroscopy, a tunable UWB pulse generator facilitates exploration of microscopic dielectric mechanisms, which contribute to dispersion characteristics. Conventional approaches to tunable pulse generator design have resulted in complex circuit topologies and unsymmetrical waveform morphologies. In this research, a new design approach for low-complexity, tunable, sub-nanosecond and UWB pulse generator was developed. This approach was applied to the development of a novel generator that produces symmetrical waveforms (patent pending 60/597,746). Next, this research addressed problems with transmission-reflection (T/R) measurement of cell suspensions. In T/R measurement, coaxial transmission line fixtures have historically required an elaborate sample holder for containing liquids, resulting in high cost and complexity. Furthermore, the algorithms used to extract T/R dielectric properties have suffered from myriad problems including local minima and halfwavelength resonance. In this dissertation, a simple coaxial transmission line fixture for holding liquids by dispensing with the air-core assumption inherent in previous designs was developed (patent pending 60/916,042). In addition, a genetic algorithm was applied towards extracting dielectric properties from measurement data to circumvent problems of local minima and half wavelength resonance. Finally, in this research the capacity for using dielectric properties to quantify isolated B16-F10 tumor cells in McCoy's liquid medium was investigated. In so doing, the utility of the Maxwell-Wagner mixture formula for cell quantification was demonstrated by measuring distinct dielectric properties for differing volumes of cell suspensions using frequency- and time-domain dielectric spectroscopy.

A Study of Moisture Sorption and Dielectric Processes of Starch and Sodium Starch Glycolate : Theme: Formulation and Manufacturing of Solid Dosage Forms Guest Editors: Tony Zhou and Tonglei Li.

PubMed

Hiew, Tze Ning; Huang, Rongying; Popov, Ivan; Feldman, Yuri; Heng, Paul Wan Sia

2017-12-01

This study explored the potential of combining the use of moisture sorption isotherms and dielectric relaxation profiles of starch and sodium starch glycolate (SSG) to probe the location of moisture in dried and hydrated samples. Starch and SSG samples, dried and hydrated, were prepared. For hydrated samples, their moisture contents were determined. The samples were probed by dielectric spectroscopy using a frequency band of 0.1 Hz to 1 MHz to investigate their moisture-related relaxation profiles. The moisture sorption and desorption isotherms of starch and SSG were generated using a vapor sorption analyzer, and modeled using the Guggenheim-Anderson-de Boer equation. A clear high frequency relaxation process was detected in both dried and hydrated starches, while for dried starch, an additional slower low frequency process was also detected. The high frequency relaxation processes in hydrated and dried starches were assigned to the coupled starch-hydrated water relaxation. The low frequency relaxation in dried starch was attributed to the local chain motions of the starch backbone. No relaxation process associated with water was detected in both hydrated and dried SSG within the frequency and temperature range used in this study. The moisture sorption isotherms of SSG suggest the presence of high energy free water, which could have masked the relaxation process of the bound water during dielectric measurements. The combined study of moisture sorption isotherms and dielectric spectroscopy was shown to be beneficial and complementary in probing the effects of moisture on the relaxation processes of starch and SSG.

Effects of Pulsed Electromagnetic Fields on Breast Cancer Cell Line MCF 7 Using Absorption Spectroscopy.

PubMed

Alcantara, Dominic Z; Soliman, Ian Jerry S; Pobre, Romeric F; Naguib, Raouf N G

2017-07-01

We present an analysis of the effects of pulsed electromagnetic fields (PEMF) with 3.3 MHz carrier frequency and modulated by audio resonant frequencies on the MCF-7 breast cancer cell line in vitro using absorption spectroscopy. This involves a fluorescence dye called PrestoBlue™ Cell Viability Reagent and a spectrophotometry to test the viability of MCF-7 breast cancer cells under different PEMF treatment conditions in terms of the cell absorption values. The DNA molecule of the MCF-7 breast cancer cells has an electric dipole property that renders it sensitive and reactive to applied electromagnetic fields. Resonant frequencies derived from four genes mutated in MCF-7 breast cancer cells [rapamycin-insensitive companion of mammalian target of rapamycin (RICTOR), peroxisome proliferator-activated receptor (PPARG), Nijmegen breakage syndrome 1 (NBN) and checkpoint kinase 2 (CHEK2)] were applied in generating square pulsed electromagnetic waves. Effects were monitored through measurement of absorption of the samples with PrestoBlue™, and the significance of the treatment was determined using the t-test. There was a significant effect on MCF-7 cells after treatment with PEMF at the resonant frequencies of the following genes for specific durations of exposure: RICTOR for 10 min, PPARG for 10 min, NBN for 15 min, and CHEK2 for 5 min. Copyright© 2017, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

Wideband THz Time Domain Spectroscopy based on Optical Rectification and Electro-Optic Sampling

PubMed Central

Tomasino, A.; Parisi, A.; Stivala, S.; Livreri, P.; Cino, A. C.; Busacca, A. C.; Peccianti, M.; Morandotti, R.

2013-01-01

We present an analytical model describing the full electromagnetic propagation in a THz time-domain spectroscopy (THz-TDS) system, from the THz pulses via Optical Rectification to the detection via Electro Optic-Sampling. While several investigations deal singularly with the many elements that constitute a THz-TDS, in our work we pay particular attention to the modelling of the time-frequency behaviour of all the stages which compose the experimental set-up. Therefore, our model considers the following main aspects: (i) pump beam focusing into the generation crystal; (ii) phase-matching inside both the generation and detection crystals; (iii) chromatic dispersion and absorption inside the crystals; (iv) Fabry-Perot effect; (v) diffraction outside, i.e. along the propagation, (vi) focalization and overlapping between THz and probe beams, (vii) electro-optic sampling. In order to validate our model, we report on the comparison between the simulations and the experimental data obtained from the same set-up, showing their good agreement. PMID:24173583

Second-harmonic generation of ZnO nanoparticles synthesized by laser ablation of solids in liquids

NASA Astrophysics Data System (ADS)

Rocha-Mendoza, Israel; Camacho-López, Santiago; Luna-Palacios, Yryx Y.; Esqueda-Barrón, Yasmín; Camacho-López, Miguel A.; Camacho-López, Marco; Aguilar, Guillermo

2018-02-01

We report the synthesis of small zinc oxide nanoparticles (ZnO NPs) based colloidal suspensions and the study of second-harmonic generation from aggregated ZnO NPs deposited on glass substrates. The colloidal suspensions were obtained using the laser ablation of solids in liquids technique, ablating a Zn solid target immersed in acetone as the liquid medium, with ns-laser pulses (1064 nm) of a Nd-YAG laser. The per pulse laser fluence, the laser repetition rate frequency and the ablation time were kept constant. The absorption evolution of the obtained suspensions was optically characterized through absorption spectroscopy until stabilization. Raman spectroscopy, SEM and HRTEM were used to provide evidence of the ZnO NPs structure. HRTEM results showed that 5-8 nm spheroids ZnO NPs were obtained. Strong second-harmonic signal is obtained from random ZnO monocrystalline NPs and from aggregated ZnO NPs, suggesting that the high efficiency of the nonlinear process may not depend on the NPs size or aggregation state.

Adsorption of 1- and 2-butylimidazoles at the copper/air and steel/air interfaces studied by sum frequency generation vibrational spectroscopy.

PubMed

Casford, Michael T L; Davies, Paul B

2012-07-24

The structure of thin films of 1- and 2-butylimidazoles adsorbed on copper and steel surfaces under air was examined using sum frequency generation (SFG) vibrational spectroscopy in the ppp and ssp polarizations. Additionally, the SFG spectra of both isomers were recorded at 55 °C at the liquid imidazole/air interface for reference. Complementary bulk infrared, reflection-absorption infrared spectroscopy (RAIRS), and Raman spectra of both imidazoles were recorded for assignment purposes. The SFG spectra in the C-H stretching region at the liquid/air interface are dominated by resonances from the methyl end group of the butyl side chain of the imidazoles, indicating that they are aligned parallel or closely parallel to the surface normal. These are also the most prominent features in the SFG spectra on copper and steel. In addition, both the ppp and ssp spectra on copper show resonances from the C-H stretching modes of the imidazole ring for both isomers. The ring C-H resonances are completely absent from the spectra on steel and at the liquid/air interface. The relative intensities of the SFG spectra can be interpreted as showing that, on copper, under air, both butylimidazoles are adsorbed with their butyl side chains perpendicular to the interface and with the ring significantly inclined away from the surface plane and toward the surface normal. The SFG spectra of both imidazoles on steel indicate an orientation where the imidazole rings are parallel or nearly parallel to the surface. The weak C-H resonances from the ring at the liquid/air interface suggest that the tilt angle of the ring from the surface normal at this interface is significantly greater than it is on copper.

Quantitative frequency-domain fluorescence spectroscopy in tissues and tissue-like media

NASA Astrophysics Data System (ADS)

Cerussi, Albert Edward

1999-09-01

In the never-ending quest for improved medical technology at lower cost, modern near-infrared optical spectroscopy offers the possibility of inexpensive technology for quantitative and non-invasive diagnoses. Hemoglobin is the dominant chromophore in the 700-900 nm spectral region and as such it allows for the optical assessment of hemoglobin concentration and tissue oxygenation by absorption spectroscopy. However, there are many other important physiologically relevant compounds or physiological states that cannot be effectively sensed via optical methods because of poor optical contrast. In such cases, contrast enhancements are required. Fluorescence spectroscopy is an attractive component of optical tissue spectroscopy. Exogenous fluorophores, as well as some endogenous ones, may furnish the desperately needed sensitivity and specificity that is lacking in near-infrared optical tissue spectroscopy. The main focus of this thesis was to investigate the generation and propagation of fluorescence photons inside tissues and tissue-like media (i.e., scattering dominated media). The standard concepts of fluorescence spectroscopy have been incorporated into a diffusion-based picture that is sometimes referred to as photon migration. The novelty of this work lies in the successful quantitative recovery of fluorescence lifetimes, absolute fluorescence quantum yields, fluorophore concentrations, emission spectra, and both scattering and absorption coefficients at the emission wavelength from a tissue-like medium. All of these parameters are sensitive to the fluorophore local environment and hence are indicators of the tissue's physiological state. One application demonstrating the capabilities of frequency-domain lifetime spectroscopy in tissue-like media is a study of the binding of ethidium bromide to bovine leukocytes in fresh milk. Ethidium bromide is a fluorescent dye that is commonly used to label DNA, and hence visualize chromosomes in cells. The lifetime of ethidium bromide increases by an order of magnitude upon binding to DNA. In this thesis, I demonstrated that the fluorescence photon migration model is capable of accurately determining the somatic cell count (SCC) in a milk sample. Although meant as a demonstration of fluorescence tissue spectroscopy, this specific problem has important implications for the dairy industry's warfare against subclinical mastitis (i.e., mammary gland inflammation), since the SCC is often used as an indication of bovine infection.

Probing Pharmaceutical Mixtures during Milling: The Potency of Low-Frequency Raman Spectroscopy in Identifying Disorder.

PubMed

Walker, Greg; Römann, Philipp; Poller, Bettina; Löbmann, Korbinian; Grohganz, Holger; Rooney, Jeremy S; Huff, Gregory S; Smith, Geoffrey P S; Rades, Thomas; Gordon, Keith C; Strachan, Clare J; Fraser-Miller, Sara J

2017-12-04

This study uses a multimodal analytical approach to evaluate the rates of (co)amorphization of milled drug and excipient and the effectiveness of different analytical methods in detecting these changes. Indomethacin and tryptophan were the model substances, and the analytical methods included low-frequency Raman spectroscopy (785 nm excitation and capable of measuring both low- (10 to 250 cm -1 ) and midfrequency (450 to 1800 cm -1 ) regimes, and a 830 nm system (5 to 250 cm -1 )), conventional (200-3000 cm -1 ) Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and X-ray powder diffraction (XRPD). The kinetics of amorphization were found to be faster for the mixture, and indeed, for indomethacin, only partial amorphization occurred (after 360 min of milling). Each technique was capable of identifying the transformations, but some, such as low-frequency Raman spectroscopy and XRPD, provided less ambiguous signatures than the midvibrational frequency techniques (conventional Raman and FTIR). The low-frequency Raman spectra showed intense phonon mode bands for the crystalline and cocrystalline samples that could be used as a sensitive probe of order. Multivariate analysis has been used to further interpret the spectral changes. Overall, this study demonstrates the potential of low-frequency Raman spectroscopy, which has several practical advantages over XRPD, for probing (dis-)order during pharmaceutical processing, showcasing its potential for future development, and implementation as an in-line process monitoring method.

Propagation of THz acoustic wave packets in GaN at room temperature

DOE PAGES

Maznev, A. A.; Hung, T.-C.; Yao, Y.-T.; ...

2018-02-05

We use femtosecond laser pulses to generate coherent longitudinal acoustic phonons at frequencies of 1–1.4 THz and study their propagation in GaN-based structures at room temperature. Two InGaN-GaN multiple-quantum-well (MQW) structures separated by a 2.3 μm-thick GaN spacer are used to simultaneously generate phonon wave packets with a central frequency determined by the period of the MQW and detect them after passing through the spacer. The measurements provide lower bounds for phonon lifetimes in GaN, which are still significantly lower than those from first principles predictions. The material Q-factor at 1 THz is found to be at least as highmore » as 900. The measurements also demonstrate a partial specular reflection from the free surface of GaN at 1.4 THz. This work shows the potential of laser-based methods for THz range phonon spectroscopy and the promise for extending the viable frequency range of GaN-based acousto-electronic devices.« less

Propagation of THz acoustic wave packets in GaN at room temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maznev, A. A.; Hung, T.-C.; Yao, Y.-T.

We use femtosecond laser pulses to generate coherent longitudinal acoustic phonons at frequencies of 1–1.4 THz and study their propagation in GaN-based structures at room temperature. Two InGaN-GaN multiple-quantum-well (MQW) structures separated by a 2.3 μm-thick GaN spacer are used to simultaneously generate phonon wave packets with a central frequency determined by the period of the MQW and detect them after passing through the spacer. The measurements provide lower bounds for phonon lifetimes in GaN, which are still significantly lower than those from first principles predictions. The material Q-factor at 1 THz is found to be at least as highmore » as 900. The measurements also demonstrate a partial specular reflection from the free surface of GaN at 1.4 THz. This work shows the potential of laser-based methods for THz range phonon spectroscopy and the promise for extending the viable frequency range of GaN-based acousto-electronic devices.« less

Probing Buffer-Gas Cooled Molecules with Direct Frequency Comb Spectroscopy in the Mid-Infrrared

NASA Astrophysics Data System (ADS)

Spaun, Ben; Changala, Bryan; Bjork, Bryce J.; Heckl, Oliver H.; Patterson, David; Doyle, John M.; Ye, Jun

2015-06-01

We present the first demonstration of cavity-enhanced direct frequency comb spectroscopy on buffer-gas cooled molecules.By coupling a mid-infrared frequency comb to a high-finesse cavity surrounding a helium buffer-gas chamber, we can gather rotationally resolved absorption spectra with high sensitivity over a broad wavelength region. The measured ˜10 K rotational and translational temperatures of buffer-gas cooled molecules drastically simplify the observed spectra, compared to those of room temperature molecules, and allow for high spectral resolution limited only by Doppler broadening (10-100 MHz). Our system allows for the extension of high-resolution spectroscopy to larger molecules, enabling detailed analysis of molecular structure and dynamics, while taking full advantage of the powerful optical properties of frequency combs. A. Foltynowicz et al. Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared application to trace detection of hydrogen peroxide. Applied Physics B, vol. 110, pp. 163-175, 2013. {D. Patterson and J. M. Doyle. Cooling molecules in a cell for FTMW spectroscopy. Molecular Physics 110, 1757-1766, 2012

Advanced Theory of Driven Birdcage Resonator with Losses for Biomedical Magnetic Resonance Imaging and Spectroscopy

PubMed Central

Novikov, Alexander

2010-01-01

A complete time-dependent physics theory of symmetric unperturbed driven Hybrid Birdcage resonator was developed for general application. In particular, the theory can be applied for RF coil engineering, computer simulations of coil-sample interaction, etc. Explicit time dependence is evaluated for different forms of driving voltage. The major steps of the solution development are shown and appropriate explanations are given. Green’s functions and spectral density formula were developed for any form of periodic driving voltage. The concept of distributed power losses based on transmission line theory is developed for evaluation of local losses of a coil. Three major types of power losses are estimated as equivalent series resistances in the circuit of the Birdcage resonator. Values of generated resistances in Legs and End-Rings are estimated. An application of the theory is shown for many practical cases. Experimental curve of B1 field polarization dependence is measured for eight-sections Birdcage coil. It was shown, that the steady-state driven resonance frequencies do not depend on damping factor unlike the free oscillation (transient) frequencies. An equivalent active resistance is generated due to interaction of RF electromagnetic field with a sample. Resistance of the conductor (enhanced by skin effect), Eddy currents and dielectric losses are the major types of losses which contribute to the values of generated resistances. A biomedical sample for magnetic resonance imaging and spectroscopy is the source of the both Eddy current and dielectric losses of a coil. As demonstrated by the theory, Eddy currents losses is the major effect of coil shielding. PMID:20869184

Counter-rotating cavity solitons in a silicon nitride microresonator

NASA Astrophysics Data System (ADS)

Joshi, Chaitanya; Klenner, Alexander; Okawachi, Yoshitomo; Yu, Mengjie; Luke, Kevin; Ji, Xingchen; Lipson, Michal; Gaeta, Alexander L.

2018-02-01

We demonstrate the generation of counter-rotating cavity solitons in a silicon nitride microresonator using a fixed, single-frequency laser. We demonstrate a dual 3-soliton state with a difference in the repetition rates of the soliton trains that can be tuned by varying the ratio of pump powers in the two directions. Such a system enables a highly compact, tunable dual comb source that can be used for applications such as spectroscopy and distance ranging.

Instruments for Optical Spectroscopy and Imaging of Correlated Spin-Orbit Phases

DTIC Science & Technology

2014-10-20

2014. "A Spatially Resolved Optical Second Harmonic Generation (SHG) Study of the Perovskite Iridate Sr2IrO4 with Bulk Sensitivity". (oral) 6...The scattering plane ( light blue) is defined by the incident (red arrow) and radiated (dark blue arrow) beams. S(P)-polarization denotes an...5d transition metal oxides, with particular emphasis on the iridate family. In a conventional SHG-RA experiment, light of frequency  is impinged

Inverse Design, Development and Characterization of Catalytic Adsorbates at Semiconductor/Liquid Interfaces

DTIC Science & Technology

2016-07-08

theoretical determination of orientation of Re(I) bipyridyl complexes for CO2 reduction on Au and on TiO2 . We have recently determined the binding...crystalline TiO2 (110) surfaces relative to (001) surfaces using vibrational sum frequency generation (SFG) spectroscopy. The SFG signal shows an...isotropic distribution with the rotation of the TiO2 (001) surface relative to the incident plane, but an anisotropic distribution with the rotation

Conformational order of n-dodecanethiol and n-dodecaneselenol monolayers on polycrystalline copper investigated by PM-IRRAS and SFG spectroscopy

NASA Astrophysics Data System (ADS)

Fonder, G.; Cecchet, F.; Peremans, A.; Thiry, P. A.; Delhalle, J.; Mekhalif, Z.

2009-08-01

Self-assembled monolayers (SAMs) of n-dodecanethiol (C 12H 25SH) and n-dodecaneselenol (C 12H 25SeH) on polycrystalline copper have been elaborated with the purpose of achieving densely packed and crystalline-like assemblies. By combining the surface sensitivity of polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) and sum-frequency generation spectroscopy (SFG), the effect of the self-assembly time (15 min, 30 min, 1 h, 2 h and 24 h) on the formation of n-dodecanethiol and n-dodecaneselenol monolayers on untreated and electrochemically reduced polycrystalline copper has been investigated. On electrochemically reduced copper, PM-IRRAS spectroscopy shows that both molecules are able to form well organized layers. SFG spectroscopy indicates that the C 12H 25SeH SAMs are slightly better ordered than those achieved with C 12H 25SH. On untreated copper, the two molecules lead to different film organizations. Both PM-IRRAS and SFG indicate that C 12H 25SH SAMs are of the same film quality as those obtained on electrochemically reduced copper. On the contrary, C 12H 25SeH monolayers are invariably poorly organized at the molecular level.

Method and apparatus for two-dimensional spectroscopy

DOEpatents

DeCamp, Matthew F.; Tokmakoff, Andrei

2010-10-12

Preferred embodiments of the invention provide for methods and systems of 2D spectroscopy using ultrafast, first light and second light beams and a CCD array detector. A cylindrically-focused second light beam interrogates a target that is optically interactive with a frequency-dispersed excitation (first light) pulse, whereupon the second light beam is frequency-dispersed at right angle orientation to its line of focus, so that the horizontal dimension encodes the spatial location of the second light pulse and the first light frequency, while the vertical dimension encodes the second light frequency. Differential spectra of the first and second light pulses result in a 2D frequency-frequency surface equivalent to double-resonance spectroscopy. Because the first light frequency is spatially encoded in the sample, an entire surface can be acquired in a single interaction of the first and second light pulses.

Low Noise Frequency Comb Sources Based on Synchronously Pumped Doubly Resonant Optical Parametric Oscillators

NASA Astrophysics Data System (ADS)

Wan, Chenchen

Optical frequency combs are coherent light sources consist of thousands of equally spaced frequency lines. Frequency combs have achieved success in applications of metrology, spectroscopy and precise pulse manipulation and control. The most common way to generate frequency combs is based on mode-locked lasers which has the output spectrum of comb structures. To generate stable frequency combs, the output from mode-locked lasers need to be phase stabilized. The whole comb lines will be stabilized if the pulse train repetition rate corresponding to comb spacing and the pulse carrier envelope offset (CEO) frequency are both stabilized. The output from a laser always has fluctuations in parameters known as noise. In laser applications, noise is an important factor to limit the performance and often need to be well controlled. For example in precision measurement such as frequency metrology and precise spectroscopy, low laser intensity and phase noise is required. In mode-locked lasers there are different types of noise like intensity noise, pulse temporal position noise also known as timing jitter, optical phase noise. In term for frequency combs, these noise dynamics is more complex and often related. Understanding the noise behavior is not only of great interest in practical applications but also help understand fundamental laser physics. In this dissertation, the noise of frequency combs and mode-locked lasers will be studied in two projects. First, the CEO frequency phase noise of a synchronously pumped doubly resonant optical parametric oscillators (OPO) will be explored. This is very important for applications of the OPO as a coherent frequency comb source. Another project will focus on the intensity noise coupling in a soliton fiber oscillator, the finding of different noise coupling in soliton pulses and the dispersive waves generated from soliton perturbation can provide very practical guidance for low noise soliton laser design. OPOs are used to generate coherent laser-like radiations at which frequency the common gain material is not available. It is also a good candidate for extend frequency comb spectral range, for comb generation, the OPO is usually pumped by a comb source thus the OPO cavity needs to be synchronized to the pump pulses. Depending on whether the signal or idle light is in resonance, the OPO could be singly or doubly resonant. The doubly resonant OPO (DOPO) has much lower lasing threshold since both signal and idle are in resonance, but it also requires more cavity stability and was historically considered unstable for operation. However, recent research has proved that the synchronously pumped doubly resonant OPO could operate even without active cavity stabilization. Moreover, when the OPO is in degenerate state where the signal and idler are identical the OPO will remain frequency stabilized because it's acting as a frequency divide-by-2 system. This makes the DOPO an excellent candidate for extending the frequency comb spectral range to mid-IR by pumping with a frequency comb at near IR wavelength. In the dissertation, first a 1 mum Yb-doped fiber oscillator will be frequency stabilized to generate a frequency comb. The repetition rate is locked indirectly by locking the Yb laser to a stabilization single frequency laser and the CEO frequency is locked by f-2f self-reference. The fully locked 1 mum comb is then used to pump a DOPO. The DOPO can operate at either degenerate or non-degenerate states by tuning its cavity length. To characterize the OPO, its output spectral, output power will be measured. More importantly the CEO frequency of the OPO will also need to be simultaneously measured in order to verify and study the self stabilization of DOPO at degeneracy. To quantify the coherence property of the DOPO, the CEO frequency noise transfer function will also be measured, the pump comb is frequency modulated with an acousto-optic modulator (AOM) and the transfer function could be measured by measuring the DOPO CEO frequency phase noise. The DOPO would be a self-locked comb source if it fully inherits the pump comb coherence. This enables measuring the CEO frequency phase noise of the unlocked DOPO comb to be compared with the pump phase noise quantitatively. In the second part of the dissertation, the intensity noise of a soliton mode-locked laser is studied. The soliton is a pulse with perfect balance of dispersion and nonlinearity so it can propagate without any change of its spectral and temporal shape. In this project, an all-fiber Er soliton laser will be build. Due to the perturbation of cavity elements such as segmental gain and loss, the soliton generate dispersive wave that co-propagates inside the cavity. Notably the dispersive wave with the same phase shift of the soliton can interfere with the soliton and produce spectral peaks known as Kelly sidebands. In this work, the spectrally resolved intensity noise coupling in the soliton laser is studied. The results reveal that most of the intensity noise from the pump is couple to the Kelly sidebands while the soliton is much quieter in terms of intensity noise. In the last part of the dissertation, the 3D wave packets generation and measurement system are introduced. A SLM-based pulse shaper and beam shaper are used to generate special 3D optical wave packets from a mode-locked fiber laser. The programmable SLM enables generation of varies beam and pulse shapes. In particular, the so called wave bullets are generated with combination of diffraction free Bessel beams and dispersion free Airy pulses. To measure the 3D wave packets, a cross-correlation interferometer is demonstrated to have the capacity to reconstruct the full 3D intensity profiles of the complex wave packets.

Understanding Protein-Interface Interactions of a Fusion Protein at Silicone Oil-Water Interface Probed by Sum Frequency Generation Vibrational Spectroscopy.

PubMed

Li, Yaoxin; Pan, Duohai; Nashine, Vishal; Deshmukh, Smeet; Vig, Balvinder; Chen, Zhan

2018-02-01

Protein adsorbed at the silicone oil-water interface can undergo a conformational change that has the potential to induce protein aggregation on storage. Characterization of the protein structures at interface is therefore critical for understanding the protein-interface interactions. In this article, we have applied sum frequency generation (SFG) spectroscopy for studying the secondary structures of a fusion protein at interface and the surfactant effect on protein adsorption to silicone oil-water interface. SFG and chiral SFG spectra from adsorbed protein in the amide I region were analyzed. The presence of beta-sheet vibrational band at 1635 cm -1 implies the protein secondary structure was likely perturbed when protein adsorbed at silicone oil interface. The time-dependent SFG study showed a significant reduction in the SFG signal of preadsorbed protein when polysorbate 20 was introduced, suggesting surfactant has stronger interaction with the interface leading to desorption of protein from the interface. In the preadsorbed surfactant and a mixture of protein/polysorbate 20, SFG analysis confirmed that surfactant can dramatically prevent the protein adsorption to silicone oil surface. This study has demonstrated the potential of SFG for providing the detailed molecular level understanding of protein conformation at interface and assessing the influence of surfactant on protein adsorption behavior. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

In Situ Potentiodynamic Analysis of the Electrolyte/Silicon Electrodes Interface Reactions - A Sum Frequency Generation Vibrational Spectroscopy Study

DOE PAGES

Horowitz, Yonatan; Han, Hui-Ling; Ross, Philip N.; ...

2015-12-11

The key factor in long-term use of batteries is the formation of an electrically insulating solid layer that allows lithium ion transport but stops further electrolyte redox reactions on the electrode surface, hence solid electrolyte interphase (SEI). In this paper, we have studied a common electrolyte, 1.0 M LiPF 6/ethylene carbonate (EC)/diethyl carbonate (DEC), reduction products on crystalline silicon (Si) electrodes in a lithium (Li) half-cell system under reaction conditions. We employed in situ sum frequency generation vibrational spectroscopy (SFG-VS) with interface sensitivity in order to probe the molecular composition of the SEI surface species under various applied potentials wheremore » electrolyte reduction is expected. We found that, with a Si(100)-hydrogen terminated wafer, a Si-ethoxy (Si-OC 2H 5) surface intermediate forms due to DEC decomposition. Our results suggest that the SEI surface composition varies depending on the termination of Si surface, i.e., the acidity of the Si surface. We provide the evidence of specific chemical composition of the SEI on the anode surface under reaction conditions. This supports an electrochemical electrolyte reduction mechanism in which the reduction of the DEC molecule to an ethoxy moiety plays a key role. Finally, these findings shed new light on the formation mechanism of SEI on Si anodes in particular and on SEI formation in general.« less

Cooperative Effects of Zwitterionic-Ionic Surfactant Mixtures on the Interfacial Water Structure Revealed by Sum Frequency Generation Vibrational Spectroscopy.

PubMed

Pan, Xuecong; Yang, Fangyuan; Chen, Shunli; Zhu, Xuefeng; Wang, Chuanyi

2018-05-08

Cooperative effects of a series of equimolar binary zwitterionic-ionic surfactant mixtures on the interfacial water structure at the air-water interfaces have been studied by sum frequency generation vibrational spectroscopy (SFG-VS). For zwitterionic surfactant palmityl sulfobetaine (SNC 16 ), anionic surfactant sodium hexadecyl sulfate (SHS), and cationic surfactant cetyltrimethylammonium bromide (CTAB) with the same length of alkyl chain, significantly enhanced ordering of interfacial water molecules was observed for the zwitterionic-anionic surfactant mixtures SNC 16 -SHS, indicating that SNC 16 interacts more strongly with SHS than with CTAB because of the strong headgroup-headgroup electrostatic attraction for SNC 16 -SHS. Meanwhile, the SFG amplitude ratio of methyl and methylene symmetric stretching modes was used to verify the stronger interaction between SNC 16 and SHS. The conformational order indicator increased from 0.64 for SNC 16 to 7.17 for SNC 16 -SHS but only 0.94 for SNC 16 -CTAB. In addition, another anionic surfactant sodium dodecyl sulfate (SDS) was introduced to study the influence of chain-chain interaction. Decreased SFG amplitude of interfacial water molecules for SNC 16 -SDS was observed. Therefore, both the headgroup-headgroup electrostatic interaction and chain-chain van der Waals attractive interaction of the surfactants play an important role in enhancing the ordering of interfacial water molecules. The results provided experimental and theoretical bases for practical applications of the surfactants.

Structure and orientation of interfacial proteins determined by sum frequency generation vibrational spectroscopy: method and application.

PubMed

Ye, Shuji; Wei, Feng; Li, Hongchun; Tian, Kangzhen; Luo, Yi

2013-01-01

In situ and real-time characterization of molecular structures and orientation of proteins at interfaces is essential to understand the nature of interfacial protein interaction. Such work will undoubtedly provide important clues to control biointerface in a desired manner. Sum frequency generation vibrational spectroscopy (SFG-VS) has been demonstrated to be a powerful technique to study the interfacial structures and interactions at the molecular level. This paper first systematically introduced the methods for the calculation of the Raman polarizability tensor, infrared transition dipole moment, and SFG molecular hyperpolarizability tensor elements of proteins/peptides with the secondary structures of α-helix, 310-helix, antiparallel β-sheet, and parallel β-sheet, as well as the methodology to determine the orientation of interfacial protein secondary structures using SFG amide I spectra. After that, recent progresses on the determination of protein structure and orientation at different interfaces by SFG-VS were then reviewed, which provides a molecular-level understanding of the structures and interactions of interfacial proteins, specially understanding the nature of driving force behind such interactions. Although this review has focused on analysis of amide I spectra, it will be expected to offer a basic idea for the spectral analysis of amide III SFG signals and other complicated molecular systems such as RNA and DNA. Copyright © 2013 Elsevier Inc. All rights reserved.

Multi-watt, multi-octave, mid-infrared femtosecond source

PubMed Central

Hussain, Syed A.; Hartung, Alexander; Zawilski, Kevin T.; Schunemann, Peter G.; Habel, Florian; Pervak, Vladimir

2018-01-01

Spectroscopy in the wavelength range from 2 to 11 μm (900 to 5000 cm−1) implies a multitude of applications in fundamental physics, chemistry, as well as environmental and life sciences. The related vibrational transitions, which all infrared-active small molecules, the most common functional groups, as well as biomolecules like proteins, lipids, nucleic acids, and carbohydrates exhibit, reveal information about molecular structure and composition. However, light sources and detectors in the mid-infrared have been inferior to those in the visible or near-infrared, in terms of power, bandwidth, and sensitivity, severely limiting the performance of infrared experimental techniques. This article demonstrates the generation of femtosecond radiation with up to 5 W at 4.1 μm and 1.3 W at 8.5 μm, corresponding to an order-of-magnitude average power increase for ultrafast light sources operating at wavelengths longer than 5 μm. The presented concept is based on power-scalable near-infrared lasers emitting at a wavelength near 1 μm, which pump optical parametric amplifiers. In addition, both wavelength tunability and supercontinuum generation are reported, resulting in spectral coverage from 1.6 to 10.2 μm with power densities exceeding state-of-the-art synchrotron sources over the entire range. The flexible frequency conversion scheme is highly attractive for both up-conversion and frequency comb spectroscopy, as well as for a variety of time-domain applications. PMID:29713685

Effects of Frequency Dependence of the External Quantum Efficiency of Perovskite Solar Cells.

PubMed

Ravishankar, Sandheep; Aranda, Clara; Boix, Pablo P; Anta, Juan A; Bisquert, Juan; Garcia-Belmonte, Germà

2018-06-07

Perovskite solar cells are known to show very long response time scales, on the order of milliseconds to seconds. This generates considerable doubt over the validity of the measured external quantum efficiency (EQE) and consequently the estimation of the short-circuit current density. We observe a variation as high as 10% in the values of the EQE of perovskite solar cells for different optical chopper frequencies between 10 and 500 Hz, indicating a need to establish well-defined protocols of EQE measurement. We also corroborate these values and obtain new insights regarding the working mechanisms of perovskite solar cells from intensity-modulated photocurrent spectroscopy measurements, identifying the evolution of the EQE over a range of frequencies, displaying a singular reduction at very low frequencies. This reduction in EQE is ascribed to additional resistive contributions hindering charge extraction in the perovskite solar cell at short-circuit conditions, which are delayed because of the concomitant large low-frequency capacitance.

Crack detection using resonant ultrasound spectroscopy

DOEpatents

Migliori, A.; Bell, T.M.; Rhodes, G.W.

1994-10-04

Method and apparatus are provided for detecting crack-like flaws in components. A plurality of exciting frequencies are generated and applied to a component in a dry condition to obtain a first ultrasonic spectrum of the component. The component is then wet with a selected liquid to penetrate any crack-like flaws in the component. The plurality of exciting frequencies are again applied to the component and a second ultrasonic spectrum of the component is obtained. The wet and dry ultrasonic spectra are then analyzed to determine the second harmonic components in each of the ultrasonic resonance spectra and the second harmonic components are compared to ascertain the presence of crack-like flaws in the component. 5 figs.

Crack detection using resonant ultrasound spectroscopy

DOEpatents

Migliori, Albert; Bell, Thomas M.; Rhodes, George W.

1994-01-01

Method and apparatus are provided for detecting crack-like flaws in components. A plurality of exciting frequencies are generated and applied to a component in a dry condition to obtain a first ultrasonic spectrum of the component. The component is then wet with a selected liquid to penetrate any crack-like flaws in the component. The plurality of exciting frequencies are again applied to the component and a second ultrasonic spectrum of the component is obtained. The wet and dry ultrasonic spectra are then analyzed to determine the second harmonic components in each of the ultrasonic resonance spectra and the second harmonic components are compared to ascertain the presence of crack-like flaws in the component.

Design and Simulation of a Birdcage Coil using CST Studio Suite for Application at 7T

NASA Astrophysics Data System (ADS)

Palau Tomas, Bernat; Li, Houmin; Anjum, M. R.

2013-12-01

This work describes the study of coils for Magnetic Resonance Imaging (MRI) applications. The principal objective is the design of a birdcage Radio Frequency (RF) coil to use in a 7 Tesla (7T) scanner. Higher strength field generates a better SNR and increased chemical shift effect, improving spectral fat suppression and spectroscopy. Moreover, a better SNR increases the spatial resolution or reduces the imaging time. This research work presented recent developments based on high field 7T design using CST studio. The birdcage coil achieves circular polarization and generates a high homogeneous radio frequency magnetic field under many conditions. Design of a Birdcage coil for a 7T to obtain the images from s mall animals (i.e. mouse). It opens the door to design and construct a Birdcage coil for a 7T to obtain human brain images. Firstly we design a birdcage coil then the results are obtained with simulator CST Wave Studio, creating a 3D model and generating a simulation. Finally the parameters are re adjusted to obtain our desired Larmor frequency 298.2 MHz for a correct operation in 7T. This research work demonstrates the theoretical results from our design and shows the designed antenna behavior.

Structure and Order of Phosphonic Acid-Based Self-Assembled Monolayers on Si(100)

PubMed Central

Dubey, Manish; Weidner, Tobias; Gamble, Lara J.; Castner, David G.

2010-01-01

Organophosphonic acid self-assembled monolayers (SAMs) on oxide surfaces have recently seen increased use in electrical and biological sensor applications. The reliability and reproducibility of these sensors require good molecular organization in these SAMs. In this regard, packing, order and alignment in the SAMs is important, as it influences the electron transport measurements. In this study, we examine the order of hydroxyl- and methyl- terminated phosphonate films deposited onto silicon oxide surfaces by the tethering by aggregation and growth method using complementary, state-of-art surface characterization tools. Near edge x-ray absorption fine structure (NEXAFS) spectroscopy and in situ sum frequency generation (SFG) spectroscopy are used to study the order of the phosphonate SAMs in vacuum and under aqueous conditions, respectively. X-ray photoelectron spectroscopy and time of flight secondary ion mass spectrometry results show that these samples form chemically intact monolayer phosphonate films. NEXAFS and SFG spectroscopy showed that molecular order exists in the octadecylphosphonic acid and 11-hydroxyundecylphosphonic acid SAMs. The chain tilt angles in these SAMs were approximately 37° and 45°, respectively. PMID:20735054

Self-generation of optical frequency comb in single section quantum dot Fabry-Perot lasers: a theoretical study.

PubMed

Bardella, Paolo; Columbo, Lorenzo Luigi; Gioannini, Mariangela

2017-10-16

Optical Frequency Comb (OFC) generated by semiconductor lasers are currently widely used in the extremely timely field of high capacity optical interconnects and high precision spectroscopy. In the last decade, several experimental evidences of spontaneous OFC generation have been reported in single section Quantum Dot (QD) lasers. Here we provide a physical understanding of these self-organization phenomena by simulating the multi-mode dynamics of a single section Fabry-Perot (FP) QD laser using a Time-Domain Traveling-Wave (TDTW) model that properly accounts for coherent radiation-matter interaction in the semiconductor active medium and includes the carrier grating generated by the optical standing wave pattern in the laser cavity. We show that the latter is the fundamental physical effect at the origin of the multi-mode spectrum appearing just above threshold. A self-mode-locking regime associated with the emission of OFC is achieved for higher bias currents and ascribed to nonlinear phase sensitive effects as Four Wave Mixing (FWM). Our results explain in detail the behaviour observed experimentally by different research groups and in different QD and Quantum Dash (QDash) devices.

Theoretical Sum Frequency Generation Spectroscopy of Peptides

PubMed Central

2015-01-01

Vibrational sum frequency generation (SFG) has become a very promising technique for the study of proteins at interfaces, and it has been applied to important systems such as anti-microbial peptides, ion channel proteins, and human islet amyloid polypeptide. Moreover, so-called “chiral” SFG techniques, which rely on polarization combinations that generate strong signals primarily for chiral molecules, have proven to be particularly discriminatory of protein secondary structure. In this work, we present a theoretical strategy for calculating protein amide I SFG spectra by combining line-shape theory with molecular dynamics simulations. We then apply this method to three model peptides, demonstrating the existence of a significant chiral SFG signal for peptides with chiral centers, and providing a framework for interpreting the results on the basis of the dependence of the SFG signal on the peptide orientation. We also examine the importance of dynamical and coupling effects. Finally, we suggest a simple method for determining a chromophore’s orientation relative to the surface using ratios of experimental heterodyne-detected signals with different polarizations, and test this method using theoretical spectra. PMID:25203677

Novel laser induced photoacoustic spectroscopy for instantaneous trace detection of explosive materials.

PubMed

El-Sharkawy, Yasser H; Elbasuney, Sherif

2017-08-01

Laser photoacoustic spectroscopy (LPAS) is an attractive technology in terms of simplicity, ruggedness, and overall sensitivity; it detects the time dependent heat generated (thermo-elastic effect) in the target via interaction with pulsed optical radiation. This study reports on novel LPAS technique that offers instant and standoff detection capabilities of trace explosives. Over the current study, light is generated using pulsed Q-switched Nd:YAG laser; the generated photoacoustic response in stimulated explosive material offers signature values that depend on the optical, thermal, and acoustical properties. The generated acoustic waves were captured using piezoelectric transducer as well as novel customized optical sensor with remotely laser interferometer probe. A digital signal processing algorithm was employed to identify explosive material signatures via calculation of characteristic optical properties (absorption coefficient), sound velocity, and frequency response of the generated photoacoustic signal. Customized LPAS technique was employed for instantaneous trace detection of three main different high explosive materials including TNT, RDX, and HMX. The main outcome of this study is that the novel customized optical sensor signals were validated with traditional piezoelectric transducer. Furthermore, the customized optical sensor offered standoff detection capabilities (10cm), fast response, high sensitivity, and enhanced signal to noise ratio. This manuscript shaded the light on the instant detection of trace explosive materials from significant standoffs using novel customized LPAS technique. Copyright © 2017 Elsevier B.V. All rights reserved.

Diamondoid synthesis by nanosecond pulsed microplasmas generated in He at atmospheric pressure

NASA Astrophysics Data System (ADS)

Stauss, Sven; Shizuno, Tomoki; Oshima, Fumito; Pai, David Z.; Terashima, Kazuo

2012-10-01

Diamondoids are sp^3 hybridized carbon nanomaterials that possess interesting properties making them attractive for biotechnology, medicine, and opto- and nanoelectronics. So far, larger diamondoids have been synthesized using the smallest diamondoid (adamantane) as a precursor. For this electric discharges and pulsed laser plasmas generated in supercritical fluids, and hot filament chemical vapor deposition have been used, but these methods are difficult to realize or very time-consuming. We have developed a more convenient approach where diamondoids are synthesized by high-voltage nanosecond pulsed microplasmas (voltage 15 kVp-p, frequency 1 Hz, pulse width 10 ns) generated in He at atmospheric pressure using point-to-plane tungsten electrodes. Adamantane was used as a precursor, and synthesis was conducted for 10^5 pulses at gas temperatures of 297, 373 and 473 K. Energy dispersive X-ray and micro-Raman spectroscopy were conducted to determine the composition of the products, and gas chromatography - mass spectra indicated the formation of diamantane. It was found that synthesis is more efficient at room temperature than at higher temperatures, and time-resolved optical emission spectroscopy suggest that the chemical reactions take place in the afterglow.

Chemical and spectroscopic characteristics of potassium white micas related to polystage evolution of the Central Western Carpathians orogenic wedge

NASA Astrophysics Data System (ADS)

Sulák, Marián; Kaindl, Reinhard; Putiš, Marián; Sitek, Jozef; Krenn, Kurt; Tóth, Ignác

2009-12-01

Potassium white micas in sheared basement and cover rocks from the Central Western Carpathians (CWC) were investigated by PL microscopy, electron microprobe (EMP) analysis, Mössbauer and micro-Raman spectroscopy. We specified chemical and spectroscopic characteristics, which allow distinction between celadonite-poor (muscovitic) and celadonite-rich (phengitic) white mica (Wmca). Wmca generations formed during a polystage evolution in changing P- T conditions ranging from the very low to medium temperatures at medium pressure within the Alpidic CWC orogenic wedge. BSE imaging, EMP analyses and X-ray element maps indicate chemical differences between muscovite and phengite, mainly in Al, Fe and Si contents. Mössbauer spectroscopy revealed their contrasting spectra, related to different hyperfine parameters, mainly of quadrupole splitting (QS of Ms: 2.6-2.7 mm/s, or 2.9-3.0 mm/s for Phg), corresponding to Fe 2+ and Fe 3+ contents. Blastomylonitic samples with a single dominating Wmca generation and finite-strain XZ sections were suitable for micro-Raman study. These data corroborate correlation between the frequencies of two vibrational modes of Wmca and Si content. The investigated Wmca generations indicate an enhanced transformation between Wmca phases in shear zones.

Rydberg-atom based radio-frequency electrometry using frequency modulation spectroscopy in room temperature vapor cells.

PubMed

Kumar, Santosh; Fan, Haoquan; Kübler, Harald; Jahangiri, Akbar J; Shaffer, James P

2017-04-17

Rydberg atom-based electrometry enables traceable electric field measurements with high sensitivity over a large frequency range, from gigahertz to terahertz. Such measurements are particularly useful for the calibration of radio frequency and terahertz devices, as well as other applications like near field imaging of electric fields. We utilize frequency modulated spectroscopy with active control of residual amplitude modulation to improve the signal to noise ratio of the optical readout of Rydberg atom-based radio frequency electrometry. Matched filtering of the signal is also implemented. Although we have reached similarly, high sensitivity with other read-out methods, frequency modulated spectroscopy is advantageous because it is well-suited for building a compact, portable sensor. In the current experiment, ∼3 µV cm^-1 Hz^-1/2 sensitivity is achieved and is found to be photon shot noise limited.

Trapped Ion Oscillation Frequencies as Sensors for Spectroscopy

PubMed Central

Vogel, Manuel; Quint, Wolfgang; Nörtershäuser, Wilfried

2010-01-01

The oscillation frequencies of charged particles in a Penning trap can serve as sensors for spectroscopy when additional field components are introduced to the magnetic and electric fields used for confinement. The presence of so-called “magnetic bottles” and specific electric anharmonicities creates calculable energy-dependences of the oscillation frequencies in the radiofrequency domain which may be used to detect the absorption or emission of photons both in the microwave and optical frequency domains. The precise electronic measurement of these oscillation frequencies therefore represents an optical sensor for spectroscopy. We discuss possible applications for precision laser and microwave spectroscopy and their role in the determination of magnetic moments and excited state life-times. Also, the trap-assisted measurement of radiative nuclear de-excitations in the X-ray domain is discussed. This way, the different applications range over more than 12 orders of magnitude in the detectable photon energies, from below μeV in the microwave domain to beyond MeV in the X-ray domain. PMID:22294921

Quantum cascade lasers as metrological tools for space optics

NASA Astrophysics Data System (ADS)

Bartalini, S.; Borri, S.; Galli, I.; Mazzotti, D.; Cancio Pastor, P.; Giusfredi, G.; De Natale, P.

2017-11-01

A distributed-feedback quantum-cascade laser working in the 4.3÷4.4 mm range has been frequency stabilized to the Lamb-dip center of a CO2 ro-vibrational transition by means of first-derivative locking to the saturated absorption signal, and its absolute frequency counted with a kHz-level precision and an overall uncertainty of 75 kHz. This has been made possible by an optical link between the QCL and a near-IR Optical Frequency Comb Synthesizer, thanks to a non-linear sum-frequency generation process with a fiber-amplified Nd:YAG laser. The implementation of a new spectroscopic technique, known as polarization spectroscopy, provides an improved signal for the locking loop, and will lead to a narrower laser emission and a drastic improvement in the frequency stability, that in principle is limited only by the stability of the optical frequency comb synthesizer (few parts in 1013). These results confirm quantum cascade lasers as reliable sources not only for high-sensitivity, but also for highprecision measurements, ranking them as optimal laser sources for space applications.

Efficient two-stage dual-beam noncollinear optical parametric amplifier

NASA Astrophysics Data System (ADS)

Cheng, Yu-Hsiang; Gao, Frank Y.; Poulin, Peter R.; Nelson, Keith A.

2018-06-01

We have constructed a noncollinear optical parametric amplifier with two signal beams amplified in the same nonlinear crystal. This dual-beam design is more energy-efficient than operating two amplifiers in parallel. The cross-talk between two beams has been characterized and discussed. We have also added a second amplification stage to enhance the output of one of the arms, which is then frequency-doubled for ultraviolet generation. This single device provides two tunable sources for ultrafast spectroscopy in the ultraviolet and visible region.

Phase-resolved two-dimensional terahertz spectroscopy - a probe of highly nonlinear light-matter interactions

NASA Astrophysics Data System (ADS)

Elsaesser, Thomas

Terahertz (THz) spectroscopy gives insight into low-frequency excitations and charge dynamics in condensed matter. So far, most experiments in a frequency range from 0.5 to 30 THz have focused on the linear THz response to determine linear absorption and disperion spectra, and/or electric conductivities. The generation of ultrashort THz transients with peak electric fields up to megavolts/cm has allowed for addressing nonlinear light-matter interactions and inducing excitations far from equilibrium. The novel method of two-dimensional THz (2D-THz) spectroscopy allows for mapping ultrafast dynamics and couplings of elementary excitations up to arbitrary nonlinear order in the electric field, both under resonant and nonresonant excitation conditions. In particular, different contributions to the overall nonlinear response are separated by dissecting it as a function of excitation and detection frequencies and for different waiting times after excitation. This talk gives an introduction in 2D-THz spectroscopy, including its recent extension to 3-pulse sequences and interaction schemes. To illustrate the potential of the method, recent results on two-phonon coherences and high-order interband excitations in the semiconductor InSb will be presented. Nonlinear THz excitation of two-phonon coherences exploits a resonance enhancement by the large electronic interband dipole of InSb and is, thus, far more efficient than linear excitation via resonant two-phonon absorption. As a second application, the nonlinear softmode response in a crystal consisting of aspirin molecules will be discussed. At moderate THz driving fields, the pronounced correlation of rotational modes of CH3 groups with collective oscillations of π-electrons drives the system into the regime of nonperturbative light-matter interaction. Nonlinear absorption around 1.1 THz leads to a blue-shifted coherent emission at 1.5 THz, revealing a dynamic breakup of the strong electron-phonon correlations.

Electron density and temperature in an atmospheric-pressure helium diffuse dielectric barrier discharge from kHz to MHz

NASA Astrophysics Data System (ADS)

Boisvert, J.-S.; Stafford, L.; Naudé, N.; Margot, J.; Massines, F.

2018-03-01

Diffuse dielectric barrier discharges are generated over a very wide range of frequencies. According to the targeted frequency, the glow, Townsend-like, hybrid, Ω and RF-α modes are sustained. In this paper, the electrical characterization of the discharge cell together with an electrical model are used to estimate the electron density from current and voltage measurements for excitation frequencies ranging from 50 kHz to 15 MHz. The electron density is found to vary from 1014 to 1017 m-3 over this frequency range. In addition, a collisional-radiative model coupled with optical emission spectroscopy is used to evaluate the electron temperature (assuming Maxwellian electron energy distribution function) in the same conditions. The time and space-averaged electron temperature is found to be about 0.3 eV in both the low-frequency and high-frequency ranges. However, in the medium-frequency range, it reaches almost twice this value as the discharge is in the hybrid mode. The hybrid mode is similar to the atmospheric-pressure glow discharge usually observed in helium DBDs at low frequency with the major difference being that the plasma is continuously sustained and is characterized by a higher power density.

Spectrally- and Time-Resolved Sum Frequency Generation (STiR-SFG): a new tool for ultrafast hydrogen bond dynamics at interfaces.

NASA Astrophysics Data System (ADS)

Benderskii, Alexander; Bordenyuk, Andrey; Weeraman, Champika

2006-03-01

The recently developed spectrally- and time-resolved Sum Frequency Generation (STiR-SFG) is a surface-selective 3-wave mixing (IR+visible) spectroscopic technique capable of measuring ultrafast spectral evolution of vibrational coherences. A detailed description of this measurement will be presented, and a noniterative method or deconvolving the laser pulses will be introduced to obtain the molecular response function. STiR-SFG, combined with the frequency-domain SFG spectroscopy, was applied to study hydrogen bonding dynamics at aqueous interfaces (D2O/CaF2). Spectral dynamics of the OD-stretch on the 50-150 fs time scale provides real-time observation of ultrafast H-bond rearrangement. Tuning the IR wavelength to the blue or red side of the OD-stretch transition, we selectively monitor the dynamics of different sub-ensembles in the distribution of the H-bond structures. The blue-side excitation (weaker H-bonding) shows monotonic red-shift of the OD-frequency. In contrast, the red-side excitation (stronger H-bonding structures) produces a blue-shift and a recursion, which may indicate the presence of an underdamped intermolecular mode of interfacial water. Effect of electrolyte concentration on the H-bond dynamics will be discussed.

Probing electronic and vibrational properties at the electrochemical interface using SFG spectroscopy: Methanol electro-oxidation on Pt(1 1 0)

NASA Astrophysics Data System (ADS)

Vidal, F.; Busson, B.; Tadjeddine, A.

2005-02-01

We report the study of methanol electro-oxidation on Pt(1 1 0) using infrared-visible sum-frequency generation (SFG) vibrational spectroscopy. The use of this technique enables to probe the vibrational and electronic properties of the interface simultaneously in situ. We have investigated the vibrational properties of the interface in the CO ads internal stretch spectral region (1700-2150 cm -1) over a wide range of potentials. The analysis of the evolution of the C-O stretch line shape, which is related to the interference between the vibrational and electronic parts of the non-linear response, with the potential allows us to show that the onset of bulk methanol oxidation corresponds to the transition from a negatively to a positively charged surface.

Effects of electrostimulation on the vastus medialis in the deoxygenation and the blood volume signals obtained by near-infrared spectroscopy

NASA Astrophysics Data System (ADS)

Verdaguer-Codina, Joan

1996-12-01

The electrotherapy field has been generated as a technique to improve the muscles of people affected by various pathologies. For this reason the electrotherapy is increasing its use as part of a treatment in muscle therapy. However there are not studies related to electrostimulation and near-IR spectroscopy. This work was designed to assess by near-IR spectroscopy the effects of electrostimulation in the vastus medialis, applying a tetanic contraction in this muscle with a compensated rectangular impulse at 100Hz, tolerating the subject 10mA of current. In the results obtained, we have not observed significant variations in the deoxygenation and blood volume signals, whereas as light change was observed comparing the calibration signals before and after to apply electrostimulation. It is postulated that electrostimulation only increases the diameter of the vessels, because the muscle doesn't do a metabolic work, and the heart rate frequency of the subject has not increased.

Wideband laser locking to an atomic reference with modulation transfer spectroscopy.

PubMed

Negnevitsky, V; Turner, L D

2013-02-11

We demonstrate that conventional modulated spectroscopy apparatus, used for laser frequency stabilization in many atomic physics laboratories, can be enhanced to provide a wideband lock delivering deep suppression of frequency noise across the acoustic range. Using an acousto-optic modulator driven with an agile oscillator, we show that wideband frequency modulation of the pump laser in modulation transfer spectroscopy produces the unique single lock-point spectrum previously demonstrated with electro-optic phase modulation. We achieve a laser lock with 100 kHz feedback bandwidth, limited by our laser control electronics. This bandwidth is sufficient to reduce frequency noise by 30 dB across the acoustic range and narrows the imputed linewidth by a factor of five.

A novel solid solution LiGa(S1–x Se x )2 for generating coherent ultrafast mid-IR sources

NASA Astrophysics Data System (ADS)

Jer Huang, Jin; Zhang, Xin Lu; Feng, Qian; Dai, Jun Feng; Andreev, Yury M.; Lanskii, Grigory V.; Grechin, Sergei G.

2018-06-01

With renewed refractive indices, the potential of a solid solution () in optical frequency conversion—especially in phase matching and group velocity matching—is theoretically investigated, together with the composition ratio limitation. It is found that the solution has excellent features for generating coherent ultrafast mid-IR sources covering 8–11 μm, which can be realized by type II down-conversion in the ba-plane with perfect group velocity matching, or type I in the bc-plane with part group velocity matching. This will have broad applications in LiDAR monitoring and precision spectroscopy, as well as life and environmental sciences.

Structural elucidation of direct analysis in real time ionized nerve agent simulants with infrared multiple photon dissociation spectroscopy.

PubMed

Rummel, Julia L; Steill, Jeffrey D; Oomens, Jos; Contreras, Cesar S; Pearson, Wright L; Szczepanski, Jan; Powell, David H; Eyler, John R

2011-06-01

Infrared multiple photon dissociation (IRMPD) was used to generate vibrational spectra of ions produced with a direct analysis in real time (DART) ionization source coupled to a 4.7 T Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The location of protonation on the nerve agent simulants diisopropyl methylphosphonate (DIMP) and dimethyl methylphosphonate (DMMP) was studied while solutions of the compounds were introduced for extended periods of time with a syringe pump. Theoretical vibrational spectra were generated with density functional theory calculations. Visual comparison of experimental mid-IR IRMPD spectra and theoretical spectra could not establish definitively if a single structure or a mixture of conformations was present for the protonated parent of each compound. However, theoretical calculations, near-ir IRMPD spectra, and frequency-to-frequency and statistical comparisons indicated that the protonation site for both DIMP and DMMP was predominantly, if not exclusively, the phosphonyl oxygen instead of one of the oxygen atoms with only single bonds.

Alkyl chain interaction at the surface of room temperature ionic liquids: systematic variation of alkyl chain length (R = C(1)-C(4), C(8)) in both cation and anion of [RMIM][R-OSO(3)] by sum frequency generation and surface tension.

PubMed

Santos, Cherry S; Baldelli, Steven

2009-01-29

The gas-liquid interface of halide-free 1,3-dialkylimidazolium alkyl sulfates [RMIM][R-OSO(3)] with R chain length from C(1)-C(4) and C(8) has been studied systematically using the surface-specific sum frequency generation (SFG) vibrational spectroscopy and surface tension measurements. From the SFG spectra, vibrational modes from the methyl group of both cation and anion are observed for all ionic liquid samples considered in the present study. These results suggest the presence of both ions at the gas-liquid interface, which is further supported by surface tension measurements. Surface tension data show a decreasing trend as the alkyl chain in the imidazolium cation is varied from methyl to butyl chain, with a specific anion. A similar trend is observed when the alkyl chain of the anion is modified and the cation is fixed.

Fundamental High-Speed Limits in Single-Molecule, Single-Cell, and Nanoscale Force Spectroscopies

PubMed Central

2016-01-01

Force spectroscopy is enhancing our understanding of single-biomolecule, single-cell, and nanoscale mechanics. Force spectroscopy postulates the proportionality between the interaction force and the instantaneous probe deflection. By studying the probe dynamics, we demonstrate that the total force acting on the probe has three different components: the interaction, the hydrodynamic, and the inertial. The amplitudes of those components depend on the ratio between the resonant frequency and the frequency at which the data are measured. A force–distance curve provides a faithful measurement of the interaction force between two molecules when the inertial and hydrodynamic components are negligible. Otherwise, force spectroscopy measurements will underestimate the value of unbinding forces. Neglecting the above force components requires the use of frequency ratios in the 50–500 range. These ratios will limit the use of high-speed methods in force spectroscopy. The theory is supported by numerical simulations. PMID:27359243

Direct phase-locking of a 8.6-μm quantum cascade laser to a mid-IR optical frequency comb: application to precision spectroscopy of N2O.

PubMed

Gambetta, Alessio; Cassinerio, Marco; Coluccelli, Nicola; Fasci, Eugenio; Castrillo, Antonio; Gianfrani, Livio; Gatti, Davide; Marangoni, Marco; Laporta, Paolo; Galzerano, Gianluca

2015-02-01

We developed a high-precision spectroscopic system at 8.6 μm based on direct heterodyne detection and phase-locking of a room-temperature quantum-cascade-laser against an harmonic, 250-MHz mid-IR frequency comb obtained by difference-frequency generation. The ∼30  dB signal-to-noise ratio of the detected beat-note together with the achieved closed-loop locking bandwidth of ∼500  kHz allows for a residual integrated phase noise of 0.78 rad (1 Hz-5 MHz), for an ultimate resolution of ∼21  kHz, limited by the measured linewidth of the mid-IR comb. The system was used to perform absolute measurement of line-center frequencies for the rotational components of the ν2 vibrational band of N2O, with a relative precision of 3×10(-10).

Two-dimensional sum-frequency generation (2D SFG) spectroscopy: Summary of principles and its application to amyloid fiber monolayers

PubMed Central

Ghosh, Ayanjeet; Ho, Jia-Jung; Serrano, Arnaldo L.; Skoff, David R.; Zhang, Tianqi; Zanni, Martin T.

2015-01-01

By adding a mid-infrared pulse shaper to a sum-frequency generation (SFG) spectrometer, we have built a 2D SFG spectrometer capable of measuring spectra analogous to 2D IR spectra but with monolayer sensitivity and SFG selection rules. In this paper, we describe the experimental apparatus and provide an introduction to 2D SFG spectroscopy to help the reader interpret 2D SFG spectra. The main aim of this manuscript is to report 2D SFG spectra of the amyloid forming peptide FGAIL. FGAIL is a critical segment of the human islet amyloid polypeptide (hIAPP or amylin) that aggregates in people with type 2 diabetes. FGAIL is catalyzed into amyloid fibers by many types of surfaces. Here, we study the structure of FGAIL upon deposition onto a gold surface covered with a self-assembled monolayer of methyl 4-mercaptobenzoate (MMB) that produces an ester coating. FGAIL deposited on bare gold does not form ordered layers. The measured 2D SFG spectrum is consistent with amyloid fiber formation, exhibiting both the parallel (a+) and perpendicular (a−) symmetry modes associated with amyloid β-sheets. Cross peaks are observed between the ester stretches of the coating and the FGAIL peptides. Simulations are presented for two possible structures of FGAIL amyloid β-sheets that illustrates the sensitivity of the 2D SFG spectra to structure and orientation. These results provide some of the first molecular insights into surface catalyzed amyloid fiber structure. PMID:25611039

Hydration of Sulphobetaine (SB) and Tetra(ethylene glycol) (EG4)-Terminated Self-Assembled Monolayers Studied by Sum Frequency Generation (SFG) Vibrational Spectroscopy

PubMed Central

Stein, M. Jeanette; Weidner, Tobias; McCrea, Keith; Castner, David G.; Ratner, Buddy D.

2010-01-01

Sum frequency generation (SFG) vibrational spectroscopy is used to study the surface and the underlying substrate of both homogeneous and mixed self-assembled monolayers (SAMs) of 11-mercaptoundecyl-1-sulphobetainethiol (HS(CH2)11N+(CH3)2(CH2)3SO3−, SB) and 1-mercapto-11-undecyl tetra(ethylene glycol) (HS(CH2)11O(CH2CH2O)4OH, EG4) with an 11-mercapto-1-undecanol (HS(CH2)11OH, MCU) diluent. SFG results on the C–H region of the dry and hydrated SAMs gave an in situ look into the molecular orientation and suggested an approach to maximize signal-to-noise ratio on these difficult to analyze hydrophilic SAMs. Vibrational fingerprint studies in the 3000–3600 cm−1 spectral range for the SAMs exposed serially to air, water, and deuterated water revealed that a layer of tightly-bound structured water was associated with the surface of a non-fouling monolayer but was not present on a hydrophobic N-undecylmercaptan (HS(CH2)10CH3, UnD) control. The percentage of water retained upon submersion in D2O correlated well with the relative amount of protein that was previously shown to absorb onto the monolayers. These results provide evidence supporting the current theory regarding the role of a tightly-bound vicinal water layer in the protein resistance of a non-fouling group. PMID:19639981

Two-dimensional sum-frequency generation (2D SFG) spectroscopy: summary of principles and its application to amyloid fiber monolayers.

PubMed

Ghosh, Ayanjeet; Ho, Jia-Jung; Serrano, Arnaldo L; Skoff, David R; Zhang, Tianqi; Zanni, Martin T

2015-01-01

By adding a mid-infrared pulse shaper to a sum-frequency generation (SFG) spectrometer, we have built a 2D SFG spectrometer capable of measuring spectra analogous to 2D IR spectra but with monolayer sensitivity and SFG selection rules. In this paper, we describe the experimental apparatus and provide an introduction to 2D SFG spectroscopy to help the reader interpret 2D SFG spectra. The main aim of this manuscript is to report 2D SFG spectra of the amyloid forming peptide FGAIL. FGAIL is a critical segment of the human islet amyloid polypeptide (hIAPP or amylin) that aggregates in people with type 2 diabetes. FGAIL is catalyzed into amyloid fibers by many types of surfaces. Here, we study the structure of FGAIL upon deposition onto a gold surface covered with a self-assembled monolayer of methyl-4-mercaptobenzoate (MMB) that produces an ester coating. FGAIL deposited on bare gold does not form ordered layers. The measured 2D SFG spectrum is consistent with amyloid fiber formation, exhibiting both the parallel (a+) and perpendicular (a-) symmetry modes associated with amyloid β-sheets. Cross peaks are observed between the ester stretches of the coating and the FGAIL peptides. Simulations are presented for two possible structures of FGAIL amyloid β-sheets that illustrate the sensitivity of the 2D SFG spectra to structure and orientation. These results provide some of the first molecular insights into surface catalyzed amyloid fiber structure.

Sum frequency generation spectroscopy of tetraalkylphosphonium ionic liquids at the air-liquid interface

NASA Astrophysics Data System (ADS)

Peñalber-Johnstone, Chariz; Adamová, Gabriela; Plechkova, Natalia V.; Bahrami, Maryam; Ghaed-Sharaf, Tahereh; Ghatee, Mohammad Hadi; Seddon, Kenneth R.; Baldelli, Steven

2018-05-01

Sum frequency generation (SFG) spectroscopy is a nonlinear vibrational spectroscopic technique used in the study of interfaces, due to its unique ability to distinguish surface molecules that have preferential ordering compared to the isotropic bulk. Here, a series of alkyltrioctylphosphonium chloride ionic liquids, systematically varied by cation structure, were characterized at the air-liquid interface by SFG. The effect on surface structure resulting from molecular variation (i.e., addition of cyano- and methoxy-functional groups) of the cation alkyl chain was investigated. SFG spectra in the C—H stretching region (2750-3100 cm-1) for [P8 8 8 n][Cl], where n = 4, 5, 8, 10, 12, or 14, showed characteristic changes as the alkyl chain length was increased. Spectral profiles for n = 4, 5, 8, or 10 appeared similar; however, when the fourth alkyl chain was sufficiently long (as in the case of n = 12 or n = 14), abrupt changes occurred in the spectra. Molecular dynamics (MD) simulation of a slab of each ionic liquid (with n = 8, 10, or 12) confirmed gauche defects, with enhancement for the long alkyl chain and an abrupt increase of gauche occurrence from n = 8 to n = 10. A comparison of the tilt angle distribution from the simulation and the SFG analysis show a broad distribution of angles. Using experimental SFG spectra in conjunction with MD simulations, a comprehensive molecular picture at the surface of this unique class of liquids is presented.

Absolute ozone densities in a radio-frequency driven atmospheric pressure plasma using two-beam UV-LED absorption spectroscopy and numerical simulations

NASA Astrophysics Data System (ADS)

Wijaikhum, A.; Schröder, D.; Schröter, S.; Gibson, A. R.; Niemi, K.; Friderich, J.; Greb, A.; Schulz-von der Gathen, V.; O'Connell, D.; Gans, T.

2017-11-01

The efficient generation of reactive oxygen species (ROS) in cold atmospheric pressure plasma jets (APPJs) is an increasingly important topic, e.g. for the treatment of temperature sensitive biological samples in the field of plasma medicine. A 13.56 MHz radio-frequency (rf) driven APPJ device operated with helium feed gas and small admixtures of oxygen (up to 1%), generating a homogeneous glow-mode plasma at low gas temperatures, was investigated. Absolute densities of ozone, one of the most prominent ROS, were measured across the 11 mm wide discharge channel by means of broadband absorption spectroscopy using the Hartley band centred at λ = 255 nm. A two-beam setup with a reference beam in Mach-Zehnder configuration is employed for improved signal-to-noise ratio allowing high-sensitivity measurements in the investigated single-pass weak-absorbance regime. The results are correlated to gas temperature measurements, deduced from the rotational temperature of the N2 (C 3 {{{\\Pi }}}u+ \\to B 3 {{{\\Pi }}}g+, υ = 0 \\to 2) optical emission from introduced air impurities. The observed opposing trends of both quantities as a function of rf power input and oxygen admixture are analysed and explained in terms of a zero-dimensional plasma-chemical kinetics simulation. It is found that the gas temperature as well as the densities of O and O2(b{}1{{{Σ }}}g+) influence the absolute O3 densities when the rf power is varied.

Enhancing photocurrent transient spectroscopy by electromagnetic modeling.

PubMed

Diesinger, H; Panahandeh-Fard, M; Wang, Z; Baillargeat, D; Soci, C

2012-05-01

The shape and duration of photocurrent transients generated by a photoconductive switch depend on both the intrinsic response of the active material and the geometry of the transmission line structure. The present electromagnetic model decouples both shape forming contributions. In contrast to previously published work, it accounts for the particular operating mode of transient spectroscopy. The objective is to increase the time resolution by two approaches, by optimizing structural response and by deconvolving it from experimental data. The switch structure is represented by an effective transimpedance onto which the active material acts as current generator. As proof of concept, the response of a standard microstrip switch is modeled and deconvolved from experimental data acquired in GaAs, yielding a single exponential material response and hence supporting the validity of the approach. Beyond compensating for the response deterioration by the structure, switch architectures can be a priori optimized with respect to frequency response. As an example, it is shown that a microstrip gap that can be deposited on materials incompatible with standard lithography reduces pulse broadening by an order of magnitude if it is provided with transitions to coplanar access lines.

Investigation of the flatband voltage (V(FB)) shift of Al2O3 on N2 plasma treated Si substrate.

PubMed

Kim, Hyungchul; Lee, Jaesang; Jeon, Heeyoung; Park, Jingyu; Jeon, Hyeongtag

2013-09-01

The relationships between the physical and electrical characteristics of films treated with N2 plasma followed by forming gas annealing (FGA) were investigated. The Si substrates were treated with various radio frequency (RF) power levels under a N2 ambient. Al2O3 films were then deposited on Si substrates via remote plasma atomic-layer deposition. The plasma characteristics, such as the radical and ion density, were investigated using optical emission spectroscopy. Through X-ray photoelectron spectroscopy, the chemical-bonding configurations of the samples treated with N2 plasma and FGA were examined. The quantity of Si-N bonds increased as the RF power was increased, and Si--O--N bonds were generated after FGA. The flatband voltage (VFB) was shifted in the negative direction with increasing RF power, but the VFB values of the samples after FGA shifted in the positive direction due to the formation of Si--O--N bonds. N2 plasma treatment with various RF power levels slightly increased the leakage current due to the generation of defect sites.

Graphene-Immobilized fac-Re(bipy)(CO)3Cl for Syngas Generation from Carbon Dioxide.

PubMed

Zhou, Xin; Micheroni, Daniel; Lin, Zekai; Poon, Christopher; Li, Zhong; Lin, Wenbin

2016-02-17

We report the synthesis of fac-M(4-amino-bipy)(CO)3X (M = Mn and X = Br or M = Re and X = Cl, with bipy = 2,2'-bipyridine), their immobilization on graphene oxide (GrO) via diazonium grafting, and the use of Re-functionalized GrO for electrocatalytic syngas production. Infrared (IR) spectroscopy, X-ray absorption fine structure (XAFS) spectroscopy, and electrocatalysis indicated successful grafting of the Re catalyst onto GrO. Re-functionalized GrO was then deposited onto a glassy carbon electrode (GCE) for CO2 reduction. Investigation of the Re-functionalized GCE for syngas production was performed in a CO2-saturated acetonitrile solution with 3.1 M H2O as the proton source and 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the supporting electrolyte. Cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatography (GC) were employed to determine its CO2-to-CO conversion performance. The Re catalyst shows a turnover frequency (TOF) for generating CO up to 4.44 s(-1) with a CO/H2 ratio of 7:5.

Broad-band frequency references in the near-infrared: Accurate dual comb spectroscopy of methane and acetylene

NASA Astrophysics Data System (ADS)

Zolot, A. M.; Giorgetta, F. R.; Baumann, E.; Swann, W. C.; Coddington, I.; Newbury, N. R.

2013-03-01

The Doppler-limited spectra of methane between 176 THz and 184 THz (5870-6130 cm-1) and acetylene between 193 THz and 199 THz (6430-6630 cm-1) are acquired via comb-tooth resolved dual comb spectroscopy with frequency accuracy traceable to atomic standards. A least squares analysis of the measured absorbance and phase line shapes provides line center frequencies with absolute accuracy of 0.2 MHz, or less than one thousandth of the room temperature Doppler width. This accuracy is verified through comparison with previous saturated absorption spectroscopy of 37 strong isolated lines of acetylene. For the methane spectrum, the center frequencies of 46 well-isolated strong lines are determined with similar high accuracy, along with the center frequencies for 1107 non-isolated lines at lower accuracy. The measured methane line-center frequencies have an uncertainty comparable to the few available laser heterodyne measurements in this region but span a much larger optical bandwidth, marking the first broad-band measurements of the methane 2ν3 region directly referenced to atomic frequency standards. This study demonstrates the promise of dual comb spectroscopy to obtain high resolution broadband spectra that are comparable to state-of-the-art Fourier-transform spectrometer measurements but with much improved frequency accuracy.Work of the US government, not subject to US copyright.

Momentum-resolved radio-frequency spectroscopy of a spin-orbit-coupled atomic Fermi gas near a Feshbach resonance in harmonic traps

NASA Astrophysics Data System (ADS)

Peng, Shi-Guo; Liu, Xia-Ji; Hu, Hui; Jiang, Kaijun

2012-12-01

We theoretically investigate the momentum-resolved radio-frequency spectroscopy of a harmonically trapped atomic Fermi gas near a Feshbach resonance in the presence of equal Rashba and Dresselhaus spin-orbit coupling. The system is qualitatively modeled as an ideal gas mixture of atoms and molecules, in which the properties of molecules, such as the wave function, binding energy, and effective mass, are determined from the two-particle solution of two interacting atoms. We calculate separately the radio-frequency response from atoms and molecules at finite temperatures by using the standard Fermi golden rule and take into account the effect of harmonic traps within local density approximation. The total radio-frequency spectroscopy is discussed as functions of temperature and spin-orbit coupling strength. Our results give a qualitative picture of radio-frequency spectroscopy of a resonantly interacting spin-orbit-coupled Fermi gas and can be directly tested in atomic Fermi gases of 40K atoms at Shanxi University and 6Li atoms at the Massachusetts Institute of Technology.

Single-tone and two-tone AM-FM spectral calculations for tunable diode laser absorption spectroscopy

NASA Technical Reports Server (NTRS)

Chou, Nee-Yin; Sachse, Glen W.

1987-01-01

A generalized theory for optical heterodyne spectroscopy with phase modulated laser radiation is used which allows the calculation of signal line shapes for frequency modulation spectroscopy of Lorentzian gas absorption lines. In particular, synthetic spectral line shapes for both single-tone and two-tone modulation of lead-salt diode lasers are presented in which the contributions from both amplitude and frequency modulations are included.

Influence of electrolytes in the QCM response: discrimination and quantification of the interference to correct microgravimetric data.

PubMed

Encarnação, João M; Stallinga, Peter; Ferreira, Guilherme N M

2007-02-15

In this work we demonstrate that the presence of electrolytes in solution generates desorption-like transients when the resonance frequency is measured. Using impedance spectroscopy analysis and Butterworth-Van Dyke (BVD) equivalent electrical circuit modeling we demonstrate that non-Kanazawa responses are obtained in the presence of electrolytes mainly due to the formation of a diffuse electric double layer (DDL) at the sensor surface, which also causes a capacitor like signal. We extend the BVD equivalent circuit by including additional parallel capacitances in order to account for such capacitor like signal. Interfering signals from electrolytes and DDL perturbations were this way discriminated. We further quantified as 8.0+/-0.5 Hz pF-1 the influence of electrolytes to the sensor resonance frequency and we used this factor to correct the data obtained by frequency counting measurements. The applicability of this approach is demonstrated by the detection of oligonucleotide sequences. After applying the corrective factor to the frequency counting data, the mass contribution to the sensor signal yields identical values when estimated by impedance analysis and frequency counting.

Re-evaluation of rhodopsin's relaxation kinetics determined from femtosecond stimulated Raman lineshapes.

PubMed

McCamant, David W

2011-07-28

This work presents a theoretical treatment of the vibrational line shape generated in a femtosecond stimulated Raman spectroscopy (FSRS) experiment under conditions in which the probed vibration undergoes a significant frequency shift during its free induction decay. This theory is applied to simulate the FSRS lineshapes previously observed in rhodopsin (Kukura et al. Science 2005, 310, 1006). The previously determined relaxation times for formation of the trans-photoproduct of rhodopsin were calculated using an incorrect equation for the time dependence of the observed frequency shifts. Here the data are reanalyzed by calculation of the corrected frequency sweep occurring during the vibrational free induction decay. It is shown that the calculated frequency shifts and general conclusions of the original work are sound but that the coherent vibrational frequency shifts of the C(10), C(11), and C(12) hydrogen-out-of-plane vibrations occur with a 140 fs time constant rather than the previously reported 325 fs time constant. This time constant provides an important constraint for models of the dynamics of the cis to trans isomerization process. © 2011 American Chemical Society

Post-discharge gas composition of a large-gap DBD in humid air by UV-Vis absorption spectroscopy

NASA Astrophysics Data System (ADS)

Moiseev, T.; Misra, N. N.; Patil, S.; Cullen, P. J.; Bourke, P.; Keener, K. M.; Mosnier, J. P.

2014-12-01

Large gap dielectric barrier discharges (DBD) provide non-thermal, non-equilibrium plasmas that can generate specific gas chemistry with enhanced bactericidal effects when working in humid air. The present study investigates the post-discharge gas composition of such plasmas operated in humid air using UV-Vis (200-800 nm) absorption spectroscopy. Absorbance spectra have been de-convoluted using direct deconvolution and iterative methods and results are correlated to the DBD electrical parameters. The high-voltage (56 and 70 kV rms) DBD plasma generated at 50 Hz frequency in a closed container over a 20 mm gap in air with relative humidity (RH) of 5-70% has been characterized by I-V and capacitive methods. The post-discharge gas composition at each RH is assessed by UV-Vis absorption spectroscopy for plasma exposure times of 15-120 s. The concentration of ozone and nitrogen oxides (O3, NO2, NO3, N2O4) increases with plasma exposure time but a strong decrease in [O3] levels is obtained with increase in RH. The decrease in [O3] and an abundance of nitrogen oxides is ascribed to high specific power densities in the closed container and to increasing RH levels. The absorbance residual following deconvolution shows a strong band at 230-270 nm consistent with the presence of pernitric acid (HNO4) and other HNOx (x = 1, 3) species. Humid air large gap DBD plasmas in closed containers generate along with O3, high levels of nitrogen oxides and HNOx (x = 1, 4) acids leading to increased bactericidal rates.

A nu-space for image correlation spectroscopy: characterization and application to measure protein transport in live cells

NASA Astrophysics Data System (ADS)

Potvin-Trottier, Laurent; Chen, Lingfeng; Horwitz, Alan Rick; Wiseman, Paul W.

2013-08-01

We introduce a new generalized theoretical framework for image correlation spectroscopy (ICS). Using this framework, we extend the ICS method in time-frequency (ν, nu) space to map molecular flow of fluorescently tagged proteins in individual living cells. Even in the presence of a dominant immobile population of fluorescent molecules, nu-space ICS (nICS) provides an unbiased velocity measurement, as well as the diffusion coefficient of the flow, without requiring filtering. We also develop and characterize a tunable frequency-filter for spatio-temporal ICS (STICS) that allows quantification of the density, the diffusion coefficient and the velocity of biased diffusion. We show that the techniques are accurate over a wide range of parameter space in computer simulation. We then characterize the retrograde flow of adhesion proteins (α6- and αLβ2-GFP integrins and mCherry-paxillin) in CHO.B2 cells plated on laminin and intercellular adhesion molecule 1 (ICAM-1) ligands respectively. STICS with a tunable frequency filter, in conjunction with nICS, measures two new transport parameters, the density and transport bias coefficient (a measure of the diffusive character of a flow/biased diffusion), showing that molecular flow in this cell system has a significant diffusive component. Our results suggest that the integrin-ligand interaction, along with the internal myosin-motor generated force, varies for different integrin-ligand pairs, consistent with previous results.

Quantifying Young's moduli of protein fibrils and particles with bimodal force spectroscopy.

PubMed

Gilbert, Jay; Charnley, Mirren; Cheng, Christopher; Reynolds, Nicholas P; Jones, Owen G

2017-10-19

Force spectroscopy is a means of obtaining mechanical information of individual nanometer-scale structures in composite materials, such as protein assemblies for use in consumer films or gels. As a recently developed force spectroscopy technique, bimodal force spectroscopy relates frequency shifts in cantilevers simultaneously excited at multiple frequencies to the elastic properties of the contacted material, yet its utility for quantitative characterization of biopolymer assemblies has been limited. In this study, a linear correlation between experimental frequency shift and Young's modulus of polymer films was used to calibrate bimodal force spectroscopy and quantify Young's modulus of two protein nanostructures: β-lactoglobulin fibrils and zein nanoparticles. Cross-sectional Young's modulus of protein fibrils was determined to be 1.6 GPa while the modulus of zein nanoparticles was determined as 854 MPa. Parallel measurement of β-lactoglobulin fibril by a competing pulsed-force technique found a higher cross-sectional Young's modulus, highlighting the importance of comparative calibration against known standards in both pulsed and bimodal force spectroscopies. These findings demonstrate a successful procedure for measuring mechanical properties of individual protein assemblies with potential use in biological or packaging applications using bimodal force spectroscopy.

Terahertz radiation in In{sub 0.38}Ga{sub 0.62}As grown on a GaAs wafer with a metamorphic buffer layer under femtosecond laser excitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ponomarev, D. S., E-mail: ponomarev-dmitr@mail.ru; Khabibullin, R. A.; Yachmenev, A. E.

The results of time-domain spectroscopy of the terahertz (THz) generation in a structure with an In{sub 0.38}Ga{sub 0.62}As photoconductive layer are presented. This structure grown by molecular-beam epitaxy on a GaAs substrate using a metamorphic buffer layer allows THz generation with a wide frequency spectrum (to 6 THz). This is due to the additional contribution of the photo-Dember effect to THz generation. The measured optical-to-terahertz conversion efficiency in this structure is 10{sup –5} at a rather low optical fluence of ~40 μJ/cm{sup 2}, which is higher than that in low-temperature grown GaAs by almost two orders of magnitude.

Molecular oxygen detection using frequency modulation diode laser spectroscopy

NASA Technical Reports Server (NTRS)

Wang, Liang-Guo; Sachse, Glen

1990-01-01

A high-sensitivity spectroscopic measurement of O2 using two-tone frequency modulation spectroscopy with a GaAlAs diode laser is presented. An oxygen sensor based on this technique would be non-intrusive, compact and possess high sensitivity and fast time response.

Coherent multi-dimensional spectroscopy at optical frequencies in a single beam with optical readout

NASA Astrophysics Data System (ADS)

Seiler, Hélène; Palato, Samuel; Kambhampati, Patanjali

2017-09-01

Ultrafast coherent multi-dimensional spectroscopies form a powerful set of techniques to unravel complex processes, ranging from light-harvesting, chemical exchange in biological systems to many-body interactions in quantum-confined materials. Yet these spectroscopies remain complex to implement at the high frequencies of vibrational and electronic transitions, thereby limiting their widespread use. Here we demonstrate the feasibility of two-dimensional spectroscopy at optical frequencies in a single beam. Femtosecond optical pulses are spectrally broadened to a relevant bandwidth and subsequently shaped into phase coherent pulse trains. By suitably modulating the phases of the pulses within the beam, we show that it is possible to directly read out the relevant optical signals. This work shows that one needs neither complex beam geometries nor complex detection schemes in order to measure two-dimensional spectra at optical frequencies. Our setup provides not only a simplified experimental design over standard two-dimensional spectrometers but its optical readout also enables novel applications in microscopy.

Submillimeter Laboratory Investigations: Spectroscopy and Collisions

NASA Technical Reports Server (NTRS)

Herbst, Eric; DeLucia, Frank C.

2002-01-01

Currently, millimeter-wave and submillimeter-wave spectroscopy is conducted in our laboratory on several different types of spectrometers. Our standard spectrometer utilizes the output of a phase-locked klystron operating in the 40-60 GHz region, which is sent into a crossed-waveguide harmonic generator, or "multiplier". The high frequency millimeter-and submillimeter-wave radiation is transmitted via quasi-optical techniques through an absorption cell and then onto a detector, which is either an InSb hot electron bolometer cooled to 1.4 K or a Si bolometer cooled to 0.3 K. The detector response is sent to a computer for measurement and analysis. The frequency range produced and detected in this manner goes from 80 GHz to upwards of 1 THz. Spectra are normally taken with source modulation, with line frequencies typically measured to an accuracy of 50-100 kHz. Higher accuracy is available when needed. Recently, we developed a new, broad-band spectrometer in our laboratory based on a free-running backward wave oscillator (BWO) of Russian manufacture as the primary source of radiation. The so-called FASSST (fast-scan submillimeter spectroscopic technique) system uses fast-scan and optical calibration methods rather than the traditional locking techniques. The output power from the BWO is split such that 90% goes into the absorption cell while 10% is coupled to a 40-meter Fabry-Perot cavity, which yields fringe? for frequency measurement. Results from this spectrometer on the spectrum of nitric acid (HNO3) show that 100 GHz of spectral data can be obtained in 5 seconds with a measurement accuracy of 50 kHz. Currently, the frequency range of the FASSST system in our laboratory is roughly 100-700 GHz.

An electronically tuned wideband probehead for NQR spectroscopy in the VHF range

NASA Astrophysics Data System (ADS)

Scharfetter, Hermann

2016-10-01

Nuclear quadrupole resonance spectroscopy is an analytical method which allows to characterize materials which contain quadrupolar nuclei, i.e. nuclei with spin ⩾1. The measurement technology is similar to that of NMR except that no static magnetic field is necessary. In contrast to NMR, however, it is frequently necessary to scan spectra with a very large bandwidth with a span of several tens of % of the central frequency so as to localize unknown peaks. Standard NMR probeheads which are typically constructed as resonators must be tuned and matched to comparatively narrow bands and must thus be re-tuned and re-matched very frequently when scanning over a whole NQR spectrum. At low frequencies up to few MHz dedicated circuits without the need for tuning and matching have been developed, but many quadrupole nuclei have transitions in the VHF range between several tens of MHz up to several hundreds of MHz. Currently available commercial NQR probeheads employ stepper motors for setting mechanically tuneable capacitors in standard NMR resonators. These yield high quality factors (Q) and thus high SNR but are relatively large and clumsy and do not allow for fast frequency sweeps. This article presents a new concept for a NQR probehead which combines a previously published no-tune no-match wideband concept for the transmit (TX) pulse with an electronically tuneable receive (RX) part employing varactor diodes. The prototype coil provides a TX frequency range of 57 MHz with a center frequency of 97.5 MHz with a return loss of ⩽-15 dB. During RX the resonator is tuned and matched automatically to the right frequency via control voltages which are read out from a previously generated lookup table, thus providing high SNR. The control voltages which bias the varactors settle very fast and allow for hopping to the next frequency point in the spectrum within less than 100 μs. Experiments with a test sample of ZnBr2 proved the feasibility of the method.

Contactless measurement of alternating current conductance in quantum Hall structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Drichko, I. L.; Diakonov, A. M.; Malysh, V. A.

2014-10-21

We report a procedure to determine the frequency-dependent conductance of quantum Hall structures in a broad frequency domain. The procedure is based on the combination of two known probeless methods—acoustic spectroscopy and microwave spectroscopy. By using the acoustic spectroscopy, we study the low-frequency attenuation and phase shift of a surface acoustic wave in a piezoelectric crystal in the vicinity of the electron (hole) layer. The electronic contribution is resolved using its dependence on a transverse magnetic field. At high frequencies, we study the attenuation of an electromagnetic wave in a coplanar waveguide. To quantitatively calibrate these data, we use themore » fact that in the quantum-Hall-effect regime the conductance at the maxima of its magnetic field dependence is determined by extended states. Therefore, it should be frequency independent in a broad frequency domain. The procedure is verified by studies of a well-characterized p-SiGe/Ge/SiGe heterostructure.« less

Quantitative Interpretation of Polarization SFG Vibrational Spectra of Air/Methanol Interface

NASA Astrophysics Data System (ADS)

Wu, Hui; Zhang, Wen-kai; Gan, Wei; Cui, Zhi-feng; Wang, Hong-fei

2006-06-01

Even though in IR and Raman spectra of liquid methanol there is always an apparent feature for the asymmetric stretching mode of the CH3 group around 2970 cm-1, this feature has not been observed in the Sum Frequency Generation Vibrational Spectroscopy (SFG-VS) in any polarizations from the air/methanol interface. Here we present a treatment based on a corrected bond additivity model to quantitatively interpret the SFG-VS of the air/methanol interface from the IR and Raman spectra of liquid methanol.

Frequency-agile, rapid scanning spectroscopy: absorption sensitivity of 2 × 10-12 cm-1 Hz-1/2 with a tunable diode laser

NASA Astrophysics Data System (ADS)

Long, D. A.; Truong, G.-W.; van Zee, R. D.; Plusquellic, D. F.; Hodges, J. T.

2014-03-01

We present ultrasensitive measurements of molecular absorption using frequency-agile rapid scanning, cavity ring-down spectroscopy with an external-cavity diode laser. A microwave source that drives an electro-optic phase modulator with a bandwidth of 20 GHz generates pairs of sidebands on the probe laser. The optical cavity provides for high sensitivity and filters the carrier and all but a single, selected sideband. Absorption spectra were acquired by stepping the tunable sideband from mode-to-mode of the ring-down cavity at a rate that was limited only by the cavity decay time. This approach allows for scanning rates of 8 kHz per cavity resonance, a minimum detectable absorption coefficient of 1.7 × 10-11 cm-1 after only 20 ms of averaging, and a noise-equivalent absorption coefficient of 1.7 × 10-12 cm-1 Hz-1/2. By comparison with cavity-enhanced laser absorption spectrometers reported in the literature, the present system is, to the best of our knowledge, among the most sensitive and has by far the highest spectrum scanning rate.

Magnesium Nanoparticle Plasmonics.

PubMed

Biggins, John S; Yazdi, Sadegh; Ringe, Emilie

2018-06-13

Nanoparticles of some metals (Cu/Ag/Au) sustain oscillations of their electron cloud called localized surface plasmon resonances (LSPRs). These resonances can occur at optical frequencies and be driven by light, generating enhanced electric fields and spectacular photon scattering. However, current plasmonic metals are rare, expensive, and have a limited resonant frequency range. Recently, much attention has been focused on earth-abundant Al, but Al nanoparticles cannot resonate in the IR. The earth-abundant Mg nanoparticles reported here surmount this limitation. A colloidal synthesis forms hexagonal nanoplates, reflecting Mg's simple hexagonal lattice. The NPs form a thin self-limiting oxide layer that renders them stable suspended in 2-propanol solution for months and dry in air for at least two week. They sustain LSPRs observable in the far-field by optical scattering spectroscopy. Electron energy loss spectroscopy experiments and simulations reveal multiple size-dependent resonances with energies across the UV, visible, and IR. The symmetry of the modes and their interaction with the underlying substrate are studied using numerical methods. Colloidally synthesized Mg thus offers a route to inexpensive, stable nanoparticles with novel shapes and resonances spanning the entire UV-vis-NIR spectrum, making them a flexible addition to the nanoplasmonics toolbox.

Surface characterization of imidazolium-based ionic liquids with cyano-functionalized anions at the gas-liquid interface using sum frequency generation spectroscopy.

PubMed

Peñalber, Chariz Y; Grenoble, Zlata; Baker, Gary A; Baldelli, Steven

2012-04-21

Advancement in the field of ionic liquid technology requires a comprehensive understanding of their surface properties, as a wide range of chemical reactions occur mainly at interfaces. As essential media currently used in several technological applications, their accurate molecular level description at the gas-liquid interface is of utmost importance. Due to the high degree of chemical information provided in the vibrational spectrum, vibrational spectroscopy gives the most detailed model for molecular structure. The inherently surface-sensitive technique, sum frequency generation (SFG) spectroscopy, in combination with bulk-sensitive vibrational spectroscopic techniques such as FTIR and Raman, has been used in this report to characterize the surface of cyano-containing ionic liquids, such as [BMIM][SCN], [BMIM][DCA], [BMIM][TCM] and [EMIM][TCB] at the gas-liquid interface. By structural variation of the anion while keeping the cation constant, emphasis on the molecular arrangement of the anion at the gas-liquid interface is reported, and its subsequent role (if any) in determining the surface molecular orientation of the cation. Vibrational modes seen in the C-H stretching region revealed the presence of the cation at the gas-liquid interface. The cation orientation is independent of the type of cyano-containing anion, however, a similar arrangement at the surface as reported in previous studies was found, with the imidazolium ring lying flat at the surface, and the alkyl chains pointing towards the gas phase. SFG results show that all three anions of varying symmetry, namely, [DCA](-) (C(2v)), [TCM](-)(D(3h)) and [TCB](-) (T(d)) in ionic liquids [BMIM]DCA], [BMIM][TCM] and [EMIM][TCB] are significantly tilted from the surface plane, while the linear [SCN](-) in [BMIM][SCN] exhibited poor ordering, as seen in the absence of its C-N stretching mode in the SFG vibrational spectra. This journal is © the Owner Societies 2012

Static FBG strain sensor with high resolution and large dynamic range by dual-comb spectroscopy.

PubMed

Kuse, Naoya; Ozawa, Akira; Kobayashi, Yohei

2013-05-06

We demonstrate a fiber Bragg grating (FBG) strain sensor with optical frequency combs. To precisely characterize the optical response of the FBG when strain is applied, dual-comb spectroscopy is used. Highly sensitive dual-comb spectroscopy of the FBG enabled strain measurements with a resolution of 34 nε. The optical spectral bandwidth of the measurement exceeds 1 THz. Compared with conventional FBG strain sensor using a continuous-wave laser that requires rather slow frequency scanning with a limited range, the dynamic range and multiplexing capability are significantly improved by using broadband dual-comb spectroscopy.

Laser frequency-offset locking based on the frequency modulation spectroscopy with higher harmonic detection

NASA Astrophysics Data System (ADS)

Wang, Anqi; Meng, Zhixin; Feng, Yanying

2017-10-01

We design a fiber electro-optic modulator (FEOM)-based laser frequency-offset locking system using frequency modulation spectroscopy (FMS) with the 3F modulation. The modulation signal and the frequency-offset control signal are simultaneously loaded on the FEOM by a mixer in order to suppress the frequency and power jitter caused by internal modulation on the current or piezoelectric ceramic transducer (PZT). It is expected to accomplish a fast locking, a widely tunable frequency-offset, a sensitive and rapid detection of narrow spectral features with the 3F modulation. The laser frequency fluctuation is limited to +/-1MHz and its overlapping Allan deviation is around 10-12 in twenty minutes, which successfully meets the requirements of the cold atom interferometer.

Adaptive real-time dual-comb spectroscopy.

PubMed

Ideguchi, Takuro; Poisson, Antonin; Guelachvili, Guy; Picqué, Nathalie; Hänsch, Theodor W

2014-02-27

The spectrum of a laser frequency comb consists of several hundred thousand equally spaced lines over a broad spectral bandwidth. Such frequency combs have revolutionized optical frequency metrology and they now hold much promise for significant advances in a growing number of applications including molecular spectroscopy. Despite an intriguing potential for the measurement of molecular spectra spanning tens of nanometres within tens of microseconds at Doppler-limited resolution, the development of dual-comb spectroscopy is hindered by the demanding stability requirements of the laser combs. Here we overcome this difficulty and experimentally demonstrate a concept of real-time dual-comb spectroscopy, which compensates for laser instabilities by electronic signal processing. It only uses free-running mode-locked lasers without any phase-lock electronics. We record spectra spanning the full bandwidth of near-infrared fibre lasers with Doppler-limited line profiles highly suitable for measurements of concentrations or line intensities. Our new technique of adaptive dual-comb spectroscopy offers a powerful transdisciplinary instrument for analytical sciences.

Adaptive real-time dual-comb spectroscopy

NASA Astrophysics Data System (ADS)

Ideguchi, Takuro; Poisson, Antonin; Guelachvili, Guy; Picqué, Nathalie; Hänsch, Theodor W.

2014-02-01

The spectrum of a laser frequency comb consists of several hundred thousand equally spaced lines over a broad spectral bandwidth. Such frequency combs have revolutionized optical frequency metrology and they now hold much promise for significant advances in a growing number of applications including molecular spectroscopy. Despite an intriguing potential for the measurement of molecular spectra spanning tens of nanometres within tens of microseconds at Doppler-limited resolution, the development of dual-comb spectroscopy is hindered by the demanding stability requirements of the laser combs. Here we overcome this difficulty and experimentally demonstrate a concept of real-time dual-comb spectroscopy, which compensates for laser instabilities by electronic signal processing. It only uses free-running mode-locked lasers without any phase-lock electronics. We record spectra spanning the full bandwidth of near-infrared fibre lasers with Doppler-limited line profiles highly suitable for measurements of concentrations or line intensities. Our new technique of adaptive dual-comb spectroscopy offers a powerful transdisciplinary instrument for analytical sciences.

Adaptive real-time dual-comb spectroscopy

PubMed Central

Ideguchi, Takuro; Poisson, Antonin; Guelachvili, Guy; Picqué, Nathalie; Hänsch, Theodor W.

2014-01-01

The spectrum of a laser frequency comb consists of several hundred thousand equally spaced lines over a broad spectral bandwidth. Such frequency combs have revolutionized optical frequency metrology and they now hold much promise for significant advances in a growing number of applications including molecular spectroscopy. Despite an intriguing potential for the measurement of molecular spectra spanning tens of nanometres within tens of microseconds at Doppler-limited resolution, the development of dual-comb spectroscopy is hindered by the demanding stability requirements of the laser combs. Here we overcome this difficulty and experimentally demonstrate a concept of real-time dual-comb spectroscopy, which compensates for laser instabilities by electronic signal processing. It only uses free-running mode-locked lasers without any phase-lock electronics. We record spectra spanning the full bandwidth of near-infrared fibre lasers with Doppler-limited line profiles highly suitable for measurements of concentrations or line intensities. Our new technique of adaptive dual-comb spectroscopy offers a powerful transdisciplinary instrument for analytical sciences. PMID:24572636

Reverse photoacoustic standoff spectroscopy

DOEpatents

Van Neste, Charles W [Kingston, TN; Senesac, Lawrence R [Knoxville, TN; Thundat, Thomas G [Knoxville, TN

2011-04-12

A system and method are disclosed for generating a reversed photoacoustic spectrum at a greater distance. A source may emit a beam to a target and a detector measures signals generated as a result of the beam being emitted on the target. By emitting a chopped/pulsed light beam to the target, it may be possible to determine the target's optical absorbance by monitoring the intensity of light collected at the detector at different wavelengths. As the wavelength of light is changed, the target may absorb or reject each optical frequency. Rejection may increase the intensity at the sensing element and absorption may decrease the intensity. Accordingly, an identifying spectrum of the target may be made with the intensity variation of the detector as a function of illuminating wavelength.

Sensitivity and resolution in frequency comb spectroscopy of buffer gas cooled polyatomic molecules

NASA Astrophysics Data System (ADS)

Changala, P. Bryan; Spaun, Ben; Patterson, David; Doyle, John M.; Ye, Jun

2016-12-01

We discuss the use of cavity-enhanced direct frequency comb spectroscopy in the mid-infrared region with buffer gas cooling of polyatomic molecules for high-precision rovibrational absorption spectroscopy. A frequency comb coupled to an optical enhancement cavity allows us to collect high-resolution, broad-bandwidth infrared spectra of translationally and rotationally cold (10-20 K) gas-phase molecules with high absorption sensitivity and fast acquisition times. The design and performance of the combined apparatus are discussed in detail. Recorded rovibrational spectra in the CH stretching region of several organic molecules, including vinyl bromide (CH_2CHBr), adamantane (C_{10}H_{16}), and diamantane (C_{14}H_{20}) demonstrate the resolution and sensitivity of this technique, as well as the intrinsic challenges faced in extending the frontier of high-resolution spectroscopy to large complex molecules.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bondarenko, A. S., E-mail: AntonBondarenko@ymail.com; Schaeffer, D. B.; Everson, E. T.

The collision-less transfer of momentum and energy from explosive debris plasma to magnetized background plasma is a salient feature of various astrophysical and space environments. While much theoretical and computational work has investigated collision-less coupling mechanisms and relevant parameters, an experimental validation of the results demands the measurement of the complex, collective electric fields associated with debris-background plasma interaction. Emission spectroscopy offers a non-interfering diagnostic of electric fields via the Stark effect. A unique experiment at the University of California, Los Angeles, that combines the Large Plasma Device (LAPD) and the Phoenix laser facility has investigated the marginally super-Alfvénic, quasi-perpendicularmore » expansion of a laser-produced carbon (C) debris plasma through a preformed, magnetized helium (He) background plasma via emission spectroscopy. Spectral profiles of the He II 468.6 nm line measured at the maximum extent of the diamagnetic cavity are observed to intensify, broaden, and develop equally spaced modulations in response to the explosive C debris, indicative of an energetic electron population and strong oscillatory electric fields. The profiles are analyzed via time-dependent Stark effect models corresponding to single-mode and multi-mode monochromatic (single frequency) electric fields, yielding temporally resolved magnitudes and frequencies. The proximity of the measured frequencies to the expected electron plasma frequency suggests the development of the electron beam-plasma instability, and a simple saturation model demonstrates that the measured magnitudes are feasible provided that a sufficiently fast electron population is generated during C debris–He background interaction. Potential sources of the fast electrons, which likely correspond to collision-less coupling mechanisms, are briefly considered.« less

Observation of Ultrafast Magnon Dynamics in Antiferromagnetic Nickel Oxide by Optical Pump-Probe and Terahertz Time-Domain Spectroscopies

NASA Astrophysics Data System (ADS)

Kohmoto, T.; Moriyasu, T.; Wakabayashi, S.; Jinn, H.; Takahara, M.; Kakita, K.

2018-01-01

We have studied the ultrafast magnon dynamics in an antiferromagnetic 3d-transition-metal monoxide, nickel oxide (NiO), using optical pump-probe spectroscopy and terahertz time-domain spectroscopy (THz-TDS). THz damped magnon oscillations were observed in the Faraday rotation signal and in the transmitted THz electric field via optical pump-probe spectroscopy and THz-TDS, respectively. The magnon signals were observed in both the optical pump-probe spectroscopy and THz-TDS experiments, which shows that both Raman- and infrared-active modes are included in the NiO magnon modes. The magnon relaxation rate observed using THz-TDS was found to be almost constant up to the Néel temperature T N (= 523 K) and to increase abruptly near that temperature. This shows that temperature-independent spin-spin relaxation dominates up to T N . In our experiment, softening of the magnon frequency near T N was clearly observed. This result shows that the optical pump-probe spectroscopy and THz-TDS have high frequency resolution and a high signal to noise ratio in the THz region. We discuss the observed temperature dependence of the magnon frequencies using three different molecular field theories. The experimental results suggest that the biquadratic contribution of the exchange interaction plays an important role in the temperature dependence of the sublattice magnetization and the magnon frequency in cubic antiferromagnetic oxides.

IR visible sum-frequency vibrational spectroscopy of Biphenyl-3 methylene thiol monolayer on gold and silver: effect of the visible wavelength on the SFG spectrum

NASA Astrophysics Data System (ADS)

Humbert, C.; Dreesen, L.; Mani, A. A.; Caudano, Y.; Lemaire, J.-J.; Thiry, P. A.; Peremans, A.

2002-04-01

We measured IR-visible sum-frequency generation spectra of CH 3-(C 6H 4) 2-(CH 2) 3-S-H (Biphenyl-3) self-assembled monolayers on a silver and a gold substrate. For the latter substrate, we observed different interference patterns between the resonant signal of the CH vibration and the non-resonant contribution of the substrate as a function of the visible beam wavelength. The non-linear response of the gold substrate is enhanced around 480 nm corresponding to the s-d interband transition. Such effect is not observed for the silver substrate the interband transition of which is located out of the investigated visible spectral range of 450-700 nm.

Breather soliton dynamics in microresonators

NASA Astrophysics Data System (ADS)

Yu, Mengjie; Jang, Jae K.; Okawachi, Yoshitomo; Griffith, Austin G.; Luke, Kevin; Miller, Steven A.; Ji, Xingchen; Lipson, Michal; Gaeta, Alexander L.

2017-02-01

The generation of temporal cavity solitons in microresonators results in coherent low-noise optical frequency combs that are critical for applications in spectroscopy, astronomy, navigation or telecommunications. Breather solitons also form an important part of many different classes of nonlinear wave systems, manifesting themselves as a localized temporal structure that exhibits oscillatory behaviour. To date, the dynamics of breather solitons in microresonators remains largely unexplored, and its experimental characterization is challenging. Here we demonstrate the excitation of breather solitons in two different microresonator platforms based on silicon nitride and on silicon. We investigate the dependence of the breathing frequency on pump detuning and observe the transition from period-1 to period-2 oscillation. Our study constitutes a significant contribution to understanding the soliton dynamics within the larger context of nonlinear science.

[Study of emission spectroscopy of OH radicals in pulsed corona discharge].

PubMed

Wei, Bo; Luo, Zhong-Yang; Xu, Fei; Zhao, Lei; Gao, Xiang; Cen, Ke-Fa

2010-02-01

In the present paper, OH radicals generated by pulsed corona discharge in humidified air, N2 and Ar in a needle-plate reactor were measured by emission spectra. With the analysis of the emission spectra, the influence of pulse peak voltage and frequency on OH radical generation was investigated in the three kinds of background gases. The influence of the gas humidity on the generation and the distribution of OH radicals in the electric field was also discussed in detail. The authors studied the influence of the gas humidity on the generation of OH radicals in the electric field by the control of accurate change in humidity, and we also studied the distribution of OH radicals in the electric field in different background gases including humidified air, N2 and Ar by the accurate change in scales. The experiment shows that the output of OH radicals grows as the pulse peak voltage and frequency grow, but the influence of gas humidity on the process of generating OH radicals by pulsed corona discharge depends on the discharge background. The rules of the generation change when the background gases change. As the humidity in the background gases grows, the amount of OH radicals grows in the air, but it grows at first and decreases at last in N2, while it decreases at first and grows at last in Ar. The distribution of OH radical shows a trend of decreasing from the needle-electrode to its circumambience.

IR/THz Double Resonance Spectroscopy Approach for Remote Chemical Detection at Atmospheric Pressure

NASA Astrophysics Data System (ADS)

Tanner, Elizabeth A.; Phillips, Dane J.; De Lucia, Frank C.; Everitt, Henry O.

2013-06-01

A remote sensing methodology based on infrared/terahertz (IR/THz) double resonance (DR) spectroscopy is shown to overcome limitations traditionally associated with either IR or THz spectroscopic approaches for detecting trace gases in an atmosphere. The applicability of IR/THz DR spectroscopy is explored by estimating the IR and THz power requirements for detecting a 100 part-per-million-meter cloud of methyl fluoride, methyl chloride, or methyl bromide at ranges up to 1km in three atmospheric windows below 0.3 THz. These prototypical molecules are used to ascertain the dependence of the DR signal-to-noise ratio on IR and THz beam power. A line-tunable CO_2 laser with 100 ps pulse duration generates a DR signature in four rotational transitions on a time scale commensurate with collisional relaxations caused by atmospheric N_2 and O_2. A continuous wave THz beam is frequency tuned to probe one of these rotational transitions so that laser-induced absorption variations in the analyte cloud are detected as temporal power fluctuations synchronized with the laser pulses. A combination of molecule-specific physics and scenario-dependent atmospheric conditions are used to predict the signal-to-noise ratio (SNR) for detecting an analyte as a function of cloud column density. A methodology is presented by which the optimal IR/THz pump/probe frequencies are identified. These estimates show the potential for low concentration chemical detection in a challenging atmospheric scenario with currently available or near term hardware components.

Tip enhanced Raman spectroscopy, DFT and PED calculations of 4″-trimethylsilylethylsulfanyl-4,4‧-di(phenyleneethynylene)benzene thiol adsorbed on silver

NASA Astrophysics Data System (ADS)

Fletcher, Melissa C.; Alexson, Dimitri M.; Moore, Martin M.; Prokes, S. M.; Glembocki, Orest; Vivoni, Alberto; McCoy, Rhonda; Mishra, Soni; Tandon, Poonam; Hosten, Charles M.

2015-11-01

Monolayers of α,ω-dithiol oligo(phenyleneethynlene) molecules are critical to the field of molecular electronics because of their abilities to form bonds with many metallic surfaces and rectify current. In this study Fourier Transformation-Raman, surface-enhanced Raman scattering (SERS) spectroscopy and Tip-enhanced Raman Spectroscopy (TERS) were used to characterize a selectively oriented self-assembled monolayer of 4″-trimethylsilylethylsulfanyl-4,4‧-bis-(phenyleneethynylene)benzenethiol (OPE‧) on silver coated nanospheres. Selective orientation was achieved by synthesizing 4″-trimethylsilylethylsulfanyl-4,4‧-bis-(phenyleneethynylene)benzene disulfide, which undergoes oxidative dissociation and covalently bonds to the metal surface. The Ag coated nanosphere surfaces were characterized by scanning electron microscopy (SEM), which showed a large area of surface charging. The SERS and TERS spectra show similar results; however, a greater enhancement was achieved with the TERS relative to the SERS spectra. Assignments of vibrational bands were based on DFT calculations performed at the B3LYP level with good agreement between theoretical and experimental values. An average percent difference of 2.5 cm-1 was obtained for the non-CH stretching frequencies and a scaling factor was not applied to theoretically generated frequencies. A red shift of the ν(C-S) peak at 1087 cm-1 was observed when OPE‧ was adsorbed on a Ag surface. Vibrations specific to the trimethylsilylethyl (TMSE) group were visible in the TERS spectra, and disappear upon deprotection.

Rapid and economical data acquisition in ultrafast frequency-resolved spectroscopy using choppers and a microcontroller.

PubMed

Guo, Liang; Monahan, Daniele M; Fleming, Graham

2016-08-08

Spectrometers and cameras are used in ultrafast spectroscopy to achieve high resolution in both time and frequency domains. Frequency-resolved signals from the camera pixels cannot be processed by common lock-in amplifiers, which have only a limited number of input channels. Here we demonstrate a rapid and economical method that achieves the function of a lock-in amplifier using mechanical choppers and a programmable microcontroller. We demonstrate the method's effectiveness by performing a frequency-resolved pump-probe measurement on the dye Nile Blue in solution.

Non-invasive vibrational SFG spectroscopy reveals that bacterial adhesion can alter the conformation of grafted "brush" chains on SAM.

PubMed

Bulard, Emilie; Guo, Ziang; Zheng, Wanquan; Dubost, Henri; Fontaine-Aupart, Marie-Pierre; Bellon-Fontaine, Marie-Noëlle; Herry, Jean-Marie; Briandet, Romain; Bourguignon, Bernard

2011-04-19

Understanding bacterial adhesion on a surface is a crucial step to design new materials with improved properties or to control biofilm formation and eradication. Sum Frequency Generation (SFG) vibrational spectroscopy has been employed to study in situ the conformational response of a self-assembled monolayer (SAM) of octadecanethiol (ODT) on a gold film to the adhesion of hydrophilic and hydrophobic ovococcoid model bacteria. The present work highlights vibrational SFG spectroscopy as a powerful and unique non-invasive biophysical technique to probe and control bacteria interaction with ordered surfaces. Indeed, the SFG vibrational spectral changes reveal different ODT SAM conformations in air and upon exposure to aqueous solution or bacterial adhesion. Furthermore, this effect depends on the bacterial cell surface properties. The SFG spectral modeling demonstrates that hydrophobic bacteria flatten the ODT SAM alkyl chain terminal part, whereas the hydrophilic ones raise this ODT SAM terminal part. Microorganism-induced alteration of grafted chains can thus affect the desired interfacial functionality, a result that should be considered for the design of new reactive materials. © 2011 American Chemical Society

Surface-segregated monolayers: a new type of ordered monolayer for surface modification of organic semiconductors.

PubMed

Wei, Qingshuo; Tajima, Keisuke; Tong, Yujin; Ye, Shen; Hashimoto, Kazuhito

2009-12-09

We report a new type of ordered monolayer for the surface modification of organic semiconductors. Fullerene derivatives with fluorocarbon chains ([6,6]-phenyl-C(61)-buryric acid 1H,1H-perfluoro-1-alkyl ester or FC(n)) spontaneously segregated as a monolayer on the surface of a [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) film during a spin-coating process from the mixture solutions, as confirmed by X-ray photoelectron spectroscopy (XPS). Ultraviolet photoelectron spectroscopy (UPS) showed the shift of ionization potentials (IPs) depending on the fluorocarbon chain length, indicating the formation of surface dipole moments. Surface-sensitive vibrational spectroscopy, sum frequency generation (SFG) revealed the ordered molecular orientations of the C(60) moiety in the surface FC(n) layers. The intensity of the SFG signals from FC(n) on the surface showed a clear odd-even effect when the length of the fluorocarbon chain was changed. This new concept of the surface-segregated monolayer provides a facile and versatile approach to modifying the surface of organic semiconductors and is applicable to various organic optoelectronic devices.

Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

PubMed Central

Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; Park, Sunkyu; Kim, Seong H.

2015-01-01

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. It was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component. PMID:26463274

Electroluminescence and other diagnostic techniques for the study of hot-electron effects in compound semiconductor devices

NASA Astrophysics Data System (ADS)

Zanoni, Enrico; Meneghesso, Gaudenzio; Menozzi, Roberto

2000-03-01

Hot electron in III-V FETs can be indirectly monitored by measuring the current coming out from the gate when the device is biased at high electric fields. This negative current is due to the collection of holes generated by impact ionization in the gate-to drain region. Electroluminescence represents a powerful tool in order to characterize not only hot electrons but also material properties. By using spatially resolved emission microscopy it is possible to show that the light due to cold electron/hole recombination is emitted between the gate and the source (low electric field region), while the contribution due to hot electrons is emitted between the gate and the drain (high electric field region). Deep-traps created in the device by hot carriers can be analysed by means of drain current deep level transient spectroscopy and by transconductance frequency dispersion. Cathodoluminescence, optical beam induced current, X-ray spectroscopy, electron energy loss spectroscopy in combination with a transmission electron microscopy are powerful tools in order to identify and localize surface modification following hot-electron stress tests.

On-chip dual-comb source for spectroscopy.

PubMed

Dutt, Avik; Joshi, Chaitanya; Ji, Xingchen; Cardenas, Jaime; Okawachi, Yoshitomo; Luke, Kevin; Gaeta, Alexander L; Lipson, Michal

2018-03-01

Dual-comb spectroscopy is a powerful technique for real-time, broadband optical sampling of molecular spectra, which requires no moving components. Recent developments with microresonator-based platforms have enabled frequency combs at the chip scale. However, the need to precisely match the resonance wavelengths of distinct high quality-factor microcavities has hindered the development of on-chip dual combs. We report the simultaneous generation of two microresonator combs on the same chip from a single laser, drastically reducing experimental complexity. We demonstrate broadband optical spectra spanning 51 THz and low-noise operation of both combs by deterministically tuning into soliton mode-locked states using integrated microheaters, resulting in narrow (<10 kHz) microwave beat notes. We further use one comb as a reference to probe the formation dynamics of the other comb, thus introducing a technique to investigate comb evolution without auxiliary lasers or microwave oscillators. We demonstrate high signal-to-noise ratio absorption spectroscopy spanning 170 nm using the dual-comb source over a 20-μs acquisition time. Our device paves the way for compact and robust spectrometers at nanosecond time scales enabled by large beat-note spacings (>1 GHz).

Ultrafast control and monitoring of material properties using terahertz pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowlan, Pamela Renee

These are a set of slides on ultrafast control and monitoring of material properties using terahertz pulses. A few of the topics covered in these slides are: How fast is a femtosecond (fs), Different frequencies probe different properties of molecules or solids, What can a THz pulse do to a material, Ultrafast spectroscopy, Generating and measuring ultrashort THz pulses, Tracking ultrafast spin dynamics in antiferromagnets through spin wave resonances, Coherent two-dimensional THz spectroscopy, and Probing vibrational dynamics at a surface. Conclusions are: Coherent two-dimensional THz spectroscopy: a powerful approach for studying coherence and dynamics of low energy resonances. Applying thismore » to graphene we investigated the very strong THz light mater interaction which dominates over scattering. Useful for studying coupled excitations in multiferroics and monitoring chemical reactions. Also, THz-pump, SHG-probe spectoscopy: an ultrafast, surface sensitive probe of atomic-scale symmetry changes and nonlinear phonon dymanics. We are using this in Bi 2Se 3 to investigate the nonlinear surface phonon dynamics. This is potentially very useful for studying catalysis.« less

Accurate formulas for interaction force and energy in frequency modulation force spectroscopy

NASA Astrophysics Data System (ADS)

Sader, John E.; Jarvis, Suzanne P.

2004-03-01

Frequency modulation atomic force microscopy utilizes the change in resonant frequency of a cantilever to detect variations in the interaction force between cantilever tip and sample. While a simple relation exists enabling the frequency shift to be determined for a given force law, the required complementary inverse relation does not exist for arbitrary oscillation amplitudes of the cantilever. In this letter we address this problem and present simple yet accurate formulas that enable the interaction force and energy to be determined directly from the measured frequency shift. These formulas are valid for any oscillation amplitude and interaction force, and are therefore of widespread applicability in frequency modulation dynamic force spectroscopy.

Localized surface plasmon resonances in nanostructures to enhance nonlinear vibrational spectroscopies: towards an astonishing molecular sensitivity

PubMed Central

2014-01-01

Summary Vibrational transitions contain some of the richest fingerprints of molecules and materials, providing considerable physicochemical information. Vibrational transitions can be characterized by different spectroscopies, and alternatively by several imaging techniques enabling to reach sub-microscopic spatial resolution. In a quest to always push forward the detection limit and to lower the number of needed vibrational oscillators to get a reliable signal or imaging contrast, surface plasmon resonances (SPR) are extensively used to increase the local field close to the oscillators. Another approach is based on maximizing the collective response of the excited vibrational oscillators through molecular coherence. Both features are often naturally combined in vibrational nonlinear optical techniques. In this frame, this paper reviews the main achievements of the two most common vibrational nonlinear optical spectroscopies, namely surface-enhanced sum-frequency generation (SE-SFG) and surface-enhanced coherent anti-Stokes Raman scattering (SE-CARS). They can be considered as the nonlinear counterpart and/or combination of the linear surface-enhanced infrared absorption (SEIRA) and surface-enhanced Raman scattering (SERS) techniques, respectively, which are themselves a branching of the conventional IR and spontaneous Raman spectroscopies. Compared to their linear equivalent, those nonlinear vibrational spectroscopies have proved to reach higher sensitivity down to the single molecule level, opening the way to astonishing perspectives for molecular analysis. PMID:25551056

Vacuum-ultraviolet lasers and spectroscopy

NASA Astrophysics Data System (ADS)

Hollenstein, U.

2012-01-01

Single-photon ionisation of most atoms and molecules requires short-wavelength radiation, typically in the vacuum-ultraviolet (VUV, λ < 200 nm) or extreme ultraviolet (XUV, λ < 105 nm) region of the electromagnetic spectrum. The first VUV and XUV radiation sources used to study molecular photoabsorption and photoionisation spectra were light sources emitting a broad continuous spectrum, such as high pressure lamps or synchrotrons. Monochromatic VUV and XUV radiation was obtained using diffraction gratings in evacuated monochromators, which resulted in a resolving power ν/Δv of at best 106 (i. e. 0.1 cm-1 at 100 000 cm-1), but more typically in the range 104-105 . The invention of the laser and the development of nonlinear optical frequency-upconversion techniques enabled the development of table-top narrow-bandwidth, coherent VUV and XUV laser sources with which VUV photoabsorption, photoionisation and photoelectron spectra of molecules can be recorded at much higher resolution, the best sources having bandwidths better than 50 MHz. Such laser sources are ideally suited to study the structure and dynamics of electronically excited states of atoms and molecules and molecular photoionisation using photoabsorption, photoionisation and photoelectron spectroscopy. This chapter presents the general principles that are exploited to generate tunable narrow-band laser radiation below 200 nm and describes spectroscopic methods such as photoabsorption spectroscopy, photoionisation spectroscopy and threshold photoelectron spectroscopy that relay on the broad tunability and narrow-bandwidth of VUV radiation sources.

Integrated Photonic Comb Generation: Applications in Coherent Communication and Sensing

NASA Astrophysics Data System (ADS)

Parker, John S.

Integrated photonics combines many optical components including lasers, modulators, waveguides, and detectors in close proximity via homogeneous (monolithic) or heterogeneous (using multiple materials) integration. This improves stability for interferometers and lasers, reduces the occurrence of unwanted reflections, and it avoids coupling losses between different components as they are on the same chip. Thus, less power is needed to compensate for these added losses, and less heat needs to be removed due to these power savings. In addition, integration allows the many components that comprise a system to be fabricated together, thereby reducing the cost per system and allowing rapid scaling in production throughput. Integrated optical combs have many applications including: metrology, THz frequency generation, arbitrary waveform generation, optical clocks, photonic analog-to-digital converters, sensing (imaging), spectroscopy, and data communication. A comb is a set of optical sources evenly spaced in frequency. Several methods of comb generation including mode-locking and optical parametric oscillation produce phase-matched optical outputs with a fixed phase relationship between the frequency lines. When the absolute frequency of a single comb line is stabilized along with the frequency spacing between comb lines, absolute phase and frequency precision can be achieved over the entire comb bandwidth. This functionality provides tremendous benefits to many applications such as coherent communication and optical sensing. The goals for this work were achieving a broad comb bandwidth and noise reduction, i.e., frequency and phase stability. Integrated mode-locked lasers on the InGaAsP/InP material platform were chosen, as they could be monolithically integrated with the wide range of highly functional and versatile photonic integrated circuits (PICs) previously demonstrated on this platform at UCSB. Gain flattening filters were implemented to increase the comb bandwidths to 2.5 THz. Active mode-locking with an RF source was used to precisely set the frequency spacing between comb lines with better than 10 Hz accuracy. An integrated optical phase-locked loop (OPLL) for the comb was designed, built, and tested. The OPLL fixed a single comb line to a stable single linewidth laser, demonstrating a ˜430 Hz FWHM optical linewidth on the locked comb line and 20º RMS phase deviation between the comb and optical reference. The free-running linewidth is 50--100 MHz, demonstrating over 50 dB improvement in optical linewidth via locking. An integrated tunable laser (SG-DBR) with an OPLL was phase-locked to a comb source with a fixed offset frequency, thus showing the potential for using a comb with SG-DBRs as a compact frequency synthesizer.

Sum frequency generation and solid-state NMR study of the structure, orientation, and dynamics of polystyrene-adsorbed peptides

PubMed Central

Weidner, Tobias; Breen, Nicholas F.; Li, Kun; Drobny, Gary P.; Castner, David G.

2010-01-01

The power of combining sum frequency generation (SFG) vibrational spectroscopy and solid-state nuclear magnetic resonance (ssNMR) spectroscopy to quantify, with site specificity and atomic resolution, the orientation and dynamics of side chains in synthetic model peptides adsorbed onto polystyrene (PS) surfaces is demonstrated in this study. Although isotopic labeling has long been used in ssNMR studies to site-specifically probe the structure and dynamics of biomolecules, the potential of SFG to probe side chain orientation in isotopically labeled surface-adsorbed peptides and proteins remains largely unexplored. The 14 amino acid leucine-lysine peptide studied in this work is known to form an α-helical secondary structure at liquid-solid interfaces. Selective, individual deuteration of the isopropyl group in each leucine residue was used to probe the orientation and dynamics of each individual leucine side chain of LKα14 adsorbed onto PS. The selective isotopic labeling methods allowed SFG analysis to determine the orientations of individual side chains in adsorbed peptides. Side chain dynamics were obtained by fitting the deuterium ssNMR line shape to specific motional models. Through the combined use of SFG and ssNMR, the dynamic trends observed for individual side chains by ssNMR have been correlated with side chain orientation relative to the PS surface as determined by SFG. This combination provides a more complete and quantitative picture of the structure, orientation, and dynamics of these surface-adsorbed peptides than could be obtained if either technique were used separately. PMID:20628016

Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kliewer, Christopher J.; Bieri, Marco; Somorjai, Gabor A.

Sum-frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to study the adsorption and hydrogenation of pyrrole over both Pt(111) and Rh(111) single-crystal surfaces at Torr pressures (3 Torr pyrrole, 30 Torr H{sub 2}) to form pyrrolidine and the minor product butylamine. Over Pt(111) at 298 K it was found that pyrrole adsorbs in an upright geometry cleaving the N-H bond to bind through the nitrogen evidenced by SFG data. Over Rh(111) at 298 K pyrrole adsorbs in a tilted geometry relative to the surface through the p-aromatic system. A pyrroline surface reaction intermediate,more » which was not detected in the gas phase, was seen by SFG during the hydrogenation over both surfaces. Significant enhancement of the reaction rate was achieved over both metal surfaces by adsorbing 1-methylpyrrole before reaction. SFG vibrational spectroscopic results indicate that reaction promotion is achieved by weakening the bonding between the N-containing products and the metal surface because of lateral interactions on the surface between 1-methylpyrrole and the reaction species, reducing the desorption energy of the products. It was found that the ring-opening product butylamine was a reaction poison over both surfaces, but this effect can be minimized by treating the catalyst surfaces with 1-methylpyrrole before reaction. The reaction rate was not enhanced with elevated temperatures, and SFG suggests desorption of pyrrole at elevated temperatures.« less

Wavelength-Modulated Differential Photoacoustic Spectroscopy (WM-DPAS): Theory of a High-Sensitivity Methodology for the Detection of Early-Stage Tumors in Tissues

NASA Astrophysics Data System (ADS)

Choi, S.; Mandelis, A.; Guo, X.; Lashkari, B.; Kellnberger, S.; Ntziachristos, V.

2015-06-01

In the field of medical diagnostics, biomedical photoacoustics (PA) is a non-invasive hybrid optical-ultrasonic imaging modality. Due to the unique hybrid capability of optical and acoustic imaging, PA imaging has risen to the frontiers of medical diagnostic procedures such as human breast cancer detection. While conventional PA imaging has been mainly carried out by a high-power pulsed laser, an alternative technology, the frequency domain biophotoacoustic radar (FD-PAR) is under intensive development. It utilizes a continuous wave optical source with the laser intensity modulated by a frequency-swept waveform for acoustic wave generation. The small amplitude of the generated acoustic wave is significantly compensated by increased signal-to-noise ratio (several orders of magnitude) using matched-filter and pulse compression correlation processing in a manner similar to radar systems. The current study introduces the theory of a novel FD-PAR modality for ultra-sensitive characterization of functional information for breast cancer imaging. The newly developed theory of wavelength-modulated differential PA spectroscopy (WM-DPAS) detection has been introduced to address angiogenesis and hypoxia monitoring, two well-known benchmarks of breast tumor formation. Based on the WM-DPAS theory, this modality efficiently suppresses background absorptions and is expected to detect very small changes in total hemoglobin concentration and oxygenation levels, thereby identifying pre-malignant tumors before they are anatomically apparent. An experimental system design for the WM-DPAS is presented and preliminary single-ended laser experimental results were obtained and compared to a limiting case of the developed theoretical formalism.

TOPICAL REVIEW: Semiconductors for terahertz photonics applications

NASA Astrophysics Data System (ADS)

Krotkus, Arūnas

2010-07-01

Generation and measurement of ultrashort, subpicosecond pulses of electromagnetic radiation with their characteristic Fourier spectra that reach far into terahertz (THz) frequency range has recently become a versatile tool of far-infrared spectroscopy and imaging. This technique, THz time-domain spectroscopy, in addition to a femtosecond pulse laser, requires semiconductor components manufactured from materials with a short photoexcited carrier lifetime, high carrier mobility and large dark resistivity. Here we will review the most important developments in the field of investigation of such materials. The main characteristics of low-temperature-grown or ion-implanted GaAs and semiconducting compounds sensitive in the wavelength ranges around 1 µm and 1.5 µm will be surveyed. The second part of the paper is devoted to the effect of surface emission of THz transients from semiconductors illuminated by femtosecond laser pulses. The main physical mechanisms leading to this emission as well as their manifestation in various crystals will be described.

Atomic Origins of the Self-Healing Function in Cement–Polymer Composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A.

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized towards defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement/polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties ofmore » these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG spectroscopy.« less

Molecular catalysis science: Perspective on unifying the fields of catalysis.

PubMed

Ye, Rong; Hurlburt, Tyler J; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2016-05-10

Colloidal chemistry is used to control the size, shape, morphology, and composition of metal nanoparticles. Model catalysts as such are applied to catalytic transformations in the three types of catalysts: heterogeneous, homogeneous, and enzymatic. Real-time dynamics of oxidation state, coordination, and bonding of nanoparticle catalysts are put under the microscope using surface techniques such as sum-frequency generation vibrational spectroscopy and ambient pressure X-ray photoelectron spectroscopy under catalytically relevant conditions. It was demonstrated that catalytic behavior and trends are strongly tied to oxidation state, the coordination number and crystallographic orientation of metal sites, and bonding and orientation of surface adsorbates. It was also found that catalytic performance can be tuned by carefully designing and fabricating catalysts from the bottom up. Homogeneous and heterogeneous catalysts, and likely enzymes, behave similarly at the molecular level. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis.

Molecular catalysis science: Perspective on unifying the fields of catalysis

PubMed Central

Ye, Rong; Hurlburt, Tyler J.; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A.

2016-01-01

Colloidal chemistry is used to control the size, shape, morphology, and composition of metal nanoparticles. Model catalysts as such are applied to catalytic transformations in the three types of catalysts: heterogeneous, homogeneous, and enzymatic. Real-time dynamics of oxidation state, coordination, and bonding of nanoparticle catalysts are put under the microscope using surface techniques such as sum-frequency generation vibrational spectroscopy and ambient pressure X-ray photoelectron spectroscopy under catalytically relevant conditions. It was demonstrated that catalytic behavior and trends are strongly tied to oxidation state, the coordination number and crystallographic orientation of metal sites, and bonding and orientation of surface adsorbates. It was also found that catalytic performance can be tuned by carefully designing and fabricating catalysts from the bottom up. Homogeneous and heterogeneous catalysts, and likely enzymes, behave similarly at the molecular level. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis. PMID:27114536

Surface Evaluation by X-Ray Photoelectron Spectroscopy of High Performance Polyimide Foams After Exposure to Oxygen Plasma

NASA Technical Reports Server (NTRS)

Melendez, Orlando; Hampton, Michael D.; Williams, Martha K.; Brown, Sylvia F.; Nelson, Gordon L.; Weiser, Erik S.

2002-01-01

Aromatic polyimides have been attractive in the aerospace and electronics industries for applications such as cryogenic insulation, flame retardant panels and structural subcomponents. Newer to the arena of polyimides is the synthesis of polyimide foams and their applications. In the present work, three different, closely related, polyimide foams developed by NASA Langley Research Center (LaRC) are studied by X-ray Photoelectron Spectroscopy (XPS) after exposure to radio frequency generated Oxygen Plasma. Although polyimide films exposure to atomic oxygen and plasma have been studied previously and reported, the data relate to films and not foams. Foams have much more surface area and thus present new information to be explored. Understanding degradation mechanisms and properties versus structure, foam versus solid is of interest and fundamental to the application and protection of foams exposed to atomic oxygen in Low Earth Orbit (LEO).

Atomic Origins of the Self-Healing Function in Cement-Polymer Composites.

PubMed

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A; Childers, M Ian; Fernandez, Carlos; Koech, Phillip K; Bennett, Wendy D; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

2018-01-24

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) vibrational spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized toward defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement-polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties of these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG vibrational spectroscopy.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pandey, Ravindra; Usui, Kota; Livingstone, Ruth A.

Ice-nucleating organisms play important roles in the environment. With their ability to induce ice formation at temperatures just below the ice melting point, bacteria such as Pseudomonas syringae attack plants through frost damage using specialized ice-nucleating proteins. Besides the impact on agriculture and microbial ecology, airborne P. syringae can affect atmospheric glaciation processes, with consequences for cloud evolution, precipitation, and climate. Biogenic ice nucleation is also relevant for artificial snow production and for biomimetic materials for controlled interfacial freezing. We use interface-specific sum frequency generation (SFG) spectroscopy to show that hydrogen bonding at the water-bacteria contact imposes structural ordering onmore » the adjacent water network. Experimental SFG data and molecular dynamics simulations demonstrate that ice active sites within P. syringae feature unique hydrophilic-hydrophobic patterns to enhance ice nucleation. Finally, the freezing transition is further facilitated by the highly effective removal of latent heat from the nucleation site, as apparent from time-resolved SFG spectroscopy.« less

Femtosecond MeV Electron Energy-Loss Spectroscopy

NASA Astrophysics Data System (ADS)

Li, R. K.; Wang, X. J.

2017-11-01

Pump-probe electron energy-loss spectroscopy (EELS) with femtosecond temporal resolution will be a transformative research tool for studying nonequilibrium chemistry and electronic dynamics of matter. In this paper, we propose a concept of femtosecond EELS utilizing mega-electron-volt electron beams from a radio-frequency (rf) photocathode source. The high acceleration gradient and high beam energy of the rf gun are critical to the generation of 10-fs electron beams, which enables an improvement of the temporal resolution by more than 1 order of magnitude beyond the state of the art. In our proposal, the "reference-beam technique" relaxes the energy stability requirement of the rf power source by roughly 2 orders of magnitude. The requirements for the electron-beam quality, photocathode, spectrometer, and detector are also discussed. Supported by particle-tracking simulations, we demonstrate the feasibility of achieving sub-electron-volt energy resolution and approximately 10-fs temporal resolution with existing or near-future hardware performance.

Two-dimensional sum-frequency generation (2D SFG) reveals structure and dynamics of a surface-bound peptide

PubMed Central

Laaser, Jennifer E.; Skoff, David R.; Ho, Jia-Jung; Joo, Yongho; Serrano, Arnaldo L.; Steinkruger, Jay D.; Gopalan, Padma; Gellman, Samuel H.; Zanni, Martin T.

2014-01-01

Surface-bound polypeptides and proteins are increasingly used to functionalize inorganic interfaces such as electrodes, but their structural characterization is exceedingly difficult with standard technologies. In this paper, we report the first two-dimensional sum-frequency generation (2D SFG) spectra of a peptide monolayer, which is collected by adding a mid-IR pulse shaper to a standard femtosecond SFG spectrometer. On a gold surface, standard FTIR spectroscopy is inconclusive about the peptide structure because of solvation-induced frequency shifts, but the 2D lineshapes, anharmonic shifts, and lifetimes obtained from 2D SFG reveal that the peptide is largely α-helical and upright. Random coil residues are also observed, which do not themselves appear in SFG spectra due to their isotropic structural distribution, but which still absorb infrared light and so can be detected by cross-peaks in 2D SFG spectra. We discuss these results in the context of peptide design. Because of the similar way in which the spectra are collected, these 2D SFG spectra can be directly compared to 2D IR spectra, thereby enabling structural interpretations of surface-bound peptides and biomolecules based on the well-studied structure/2D IR spectra relationships established from soluble proteins. PMID:24372101

A novel nonlinear damage resonance intermodulation effect for structural health monitoring

NASA Astrophysics Data System (ADS)

Ciampa, Francesco; Scarselli, Gennaro; Meo, Michele

2017-04-01

This paper is aimed at developing a theoretical model able to predict the generation of nonlinear elastic effects associated to the interaction of ultrasonic waves with the steady-state nonlinear response of local defect resonance (LDR). The LDR effect is used in nonlinear elastic wave spectroscopy to enhance the excitation of the material damage at its local resonance, thus to dramatically increase the vibrational amplitude of material nonlinear phenomena. The main result of this work is to prove both analytically and experimentally the generation of novel nonlinear elastic wave effects, here named as nonlinear damage resonance intermodulation, which correspond to a nonlinear intermodulation between the driving frequency and the LDR one. Beside this intermodulation effect, other nonlinear elastic wave phenomena such as higher harmonics of the input frequency and superharmonics of LDR frequency were found. The analytical model relies on solving the nonlinear equation of motion governing bending displacement under the assumption of both quadratic and cubic nonlinear defect approximation. Experimental tests on a damaged composite laminate confirmed and validated these predictions and showed that using continuous periodic excitation, the nonlinear structural phenomena associated to LDR could also be featured at locations different from the damage resonance. These findings will provide new opportunities for material damage detection using nonlinear ultrasounds.

Microwave Assisted Helicon Plasmas

NASA Astrophysics Data System (ADS)

McKee, John; Caron, David; Jemiolo, Andrew; Scime, Earl

2017-10-01

The use of two (or more) rf sources at different frequencies is a common technique in the plasma processing industry to control ion energy characteristics separately from plasma generation. A similar approach is presented here with the focus on modifying the electron population in argon and helium plasmas. The plasma is generated by a helicon source at a frequency f0 = 13.56 MHz. Microwaves of frequency f1 = 2.45 GHz are then injected into the helicon source chamber perpendicular to the background magnetic field. The microwaves damp on the electrons via X-mode Electron Cyclotron Heating (ECH) at the upper hybrid resonance, providing additional energy input into the electrons. The effects of this secondary-source heating on electron density, temperature, and energy distribution function are examined and compared to helicon-only single source plasmas as well as numeric models suggesting that the heating is not evenly distributed. Optical Emission Spectroscopy (OES) is used to examine the impact of the energetic tail of the electron distribution on ion and neutral species via collisional excitation. Large enhancements of neutral spectral lines are observed in both Ar and He. While small enhancement of ion lines is seen in Ar, ion lines not normally present in He are observed during microwave injection. U.S. National Science Foundation Grant No. PHY-1360278.

Frequency Comb Spectroscopy - From IR to XUV

DTIC Science & Technology

2015-06-09

time resolution of 25 s. Publications: [1] A. Cingöz, Yost, D. C. , Allison, T. K. , Ruehl, A. , Fermann, M. E. , Hartl , I. , and Ye, J...J. , Eikema, K. S. E. , Fermann, M. E. , Hartl , I. , and Ye, J. , “Full phase stabilization of a Yb:fiber femtosecond frequency comb via high...D. C. , Allison, T. K. , Ruehl, A. , Fermann, M. E. , Hartl , I. , and Ye, J. , “Direct frequency comb spectroscopy in the extreme ultraviolet”, Nature

Broadband monolithic extractors for terahertz quantum cascade laser based frequency combs (Conference Presentation)

NASA Astrophysics Data System (ADS)

Rösch, Markus; Benea-Chelmus, Ileana-Cristina; Scalari, Giacomo; Bonzon, Christopher B.; Süess, Martin J.; Beck, Mattias; Faist, Jérôme

2017-02-01

Recent work has been showing the possibility of generating frequency combs at terahertz frequencies using terahertz quantum cascade lasers. The main efforts so far were on getting the laser to work in a stable comb operation over an as broad as possible spectral bandwidth. Another issue is the scattered farfield of such combs due to their subwavelength facets of the used metal-metal waveguide. In contrast to single mode lasers the monolithic approaches of distributed feedback lasers or photonic crystals cannot be used. We present here a monolithic broadband extractor compatible with frequency comb operation based on the concept of an end-fire antenna. The antenna can be fabricated using standard fabrication techniques. It has been designed to support a bandwidth of up to 600 GHz at a central frequency of 2.5 THz. The fabricated devices show single lobed farfields with only minor asymmetries, increased output power along an increased dynamical range of frequency comb operation. A side-absorber schematics using a thin film of Nickel has been used to suppress any higher-order lateral modes in the laser. The reported frequency combs with monolithic extractors are ideal candidates for spectroscopic applications at terahertz frequencies using a self-detected dual-comb spectroscopy setup due to the increased dynamical range along with the improved farfield leading to more output power of the frequency combs.

Passive Optical Locking Techniques for Diode Lasers

NASA Astrophysics Data System (ADS)

Zhang, Quan

1995-01-01

Most current diode-based nonlinear frequency converters utilize electronic frequency locking techniques. However, this type of locking technique typically involves very complex electronics, and suffers the 'power-drop' problem. This dissertation is devoted to the development of an all-optical passive locking technique that locks the diode laser frequency to the external cavity resonance stably without using any kind of electronic servo. The amplitude noise problem associated with the strong optical locking has been studied. Single-mode operation of a passively locked single-stripe diode with an amplitude stability better than 1% has been achieved. This passive optical locking technique applies to broad-area diodes as well as single-stripe diodes, and can be easily used to generate blue light. A schematic of a milliwatt level blue laser based on the single-stripe diode locking technique has been proposed. A 120 mW 467 nm blue laser has been built using the tapered amplifier locking technique. In addition to diode-based blue lasers, this passive locking technique has applications in nonlinear frequency conversions, resonant spectroscopy, particle counter devices, telecommunications, and medical devices.

Frequency accurate coherent electro-optic dual-comb spectroscopy in real-time.

PubMed

Martín-Mateos, Pedro; Jerez, Borja; Largo-Izquierdo, Pedro; Acedo, Pablo

2018-04-16

Electro-optic dual-comb spectrometers have proved to be a promising technology for sensitive, high-resolution and rapid spectral measurements. Electro-optic combs possess very attractive features like simplicity, reliability, bright optical teeth, and typically moderate but quickly tunable optical spans. Furthermore, in a dual-comb arrangement, narrowband electro-optic combs are generated with a level of mutual coherence that is sufficiently high to enable optical multiheterodyning without inter-comb stabilization or signal processing systems. However, this valuable tool still presents several limitations; for instance, on most systems, absolute frequency accuracy and long-term stability cannot be guaranteed; likewise, interferometer-induced phase noise restricts coherence time and limits the attainable signal-to-noise ratio. In this paper, we address these drawbacks and demonstrate a cost-efficient absolute electro-optic dual-comb instrument based on a frequency stabilization mechanism and a novel adaptive interferogram acquisition approach devised for electro-optic dual-combs capable of operating in real-time. The spectrometer, completely built from commercial components, provides sub-ppm frequency uncertainties and enables a signal-to-noise ratio of 10000 (intensity noise) in 30 seconds of integration time.

Scanning micro-resonator direct-comb absolute spectroscopy

PubMed Central

Gambetta, Alessio; Cassinerio, Marco; Gatti, Davide; Laporta, Paolo; Galzerano, Gianluca

2016-01-01

Direct optical Frequency Comb Spectroscopy (DFCS) is proving to be a fundamental tool in many areas of science and technology thanks to its unique performance in terms of ultra-broadband, high-speed detection and frequency accuracy, allowing for high-fidelity mapping of atomic and molecular energy structure. Here we present a novel DFCS approach based on a scanning Fabry-Pérot micro-cavity resonator (SMART) providing a simple, compact and accurate method to resolve the mode structure of an optical frequency comb. The SMART approach, while drastically reducing system complexity, allows for a straightforward absolute calibration of the optical-frequency axis with an ultimate resolution limited by the micro-resonator resonance linewidth and can be used in any spectral region from UV to THz. We present an application to high-precision spectroscopy of acetylene at 1.54 μm, demonstrating performances comparable or even better than current state-of-the-art DFCS systems in terms of sensitivity, optical bandwidth and frequency-resolution. PMID:27752132

Vibrational Dynamics of Interfacial Water by Free Induction Decay Sum Frequency Generation (FID-SFG) at the Al2O3(1120)/H2O Interface.

PubMed

Boulesbaa, Abdelaziz; Borguet, Eric

2014-02-06

The dephasing dynamics of a vibrational coherence may reveal the interactions of chemical functional groups with their environment. To investigate this process at a surface, we employ free induction decay sum frequency generation (FID-SFG) to measure the time that it takes for free OH stretch oscillators at the charged (pH ≈ 13, KOH) interface of alumina/water (Al2O3/H2O) to lose their collective coherence. By employing noncollinear optical parametric amplification (NOPA) technology and nonlinear vibrational spectroscopy, we showed that the single free OH peak actually corresponds to two distinct oscillators oriented opposite to each other and measured the total dephasing time, T2, of the free OH stretch modes at the Al2O3/H2O interface with a sub-40 fs temporal resolution. Our results suggested that the free OH oscillators associated with interfacial water dephase on the time scale of 89.4 ± 6.9 fs, whereas the homogeneous dephasing of interfacial alumina hydroxyls is an order of magnitude slower.

Sum Frequency Generation Spectroscopy and Molecular Dynamics Simulations Reveal a Rotationally Fluid Adsorption State of α-Pinene on Silica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, Junming; Psciuk, Brian T.; Chase, Hilary M.

2016-06-16

A rotationally fluid state of α-pinene at fused silica/vapor interfaces is revealed by computational and experimental vibrational sum frequency generation (SFG) studies. We report the first assignment of the vibrational modes in the notoriously congested C-H stretching region of α-pinene and identify its bridge methylene group on the four-membered ring ("βCH2") as the origin of its dominant spectral feature. We find that the spectra are perfused with Fermi resonances that need to be accounted for explicitly in the computation of vibrational spectra of strained hydrocarbons such α-pinene. The preferred orientations of α-pinene are consistent with optimization of van der Waalsmore » contacts with the silica surface that results in a bimodal distribution of highly fluxional orientations in which the βCH2 group points "towards" or "away from” the surface. The reported findings are particularly relevant to the exposure of α-pinene to primary oxidants in heterogeneous catalytic pathways that exploit α-pinene as a sustainable feedstock for fine chemicals and polymers.« less

Effects of strong laser fields on hadronic helium atoms

NASA Astrophysics Data System (ADS)

Lee, Han-Chieh; Jiang, Tsin-Fu

2015-12-01

The metastable hadronic helium atoms in microseconds lifetime are available in laboratory, and two-photon spectroscopy was reported recently. This exotic helium atom has an electron in the ground state and a negative hadron rotating around the helium nucleus. We theoretically study the excitation on hadronic helium by femtosecond pulse and elucidate the influence of moleculelike structure and rotation behavior on the photoelectron spectra and high-order harmonic generation. Because of the moleculelike structure, the electronic ground state consists of several angular orbitals. These angular orbitals can enhance photoelectron spectra at high energies, and also influence the harmonic generation spectra considerably. In particular, the harmonic spectra can occur at even harmonic orders because of the transition between these angular orbitals and continuum states. On the other side, the rotation behavior of hadron can induce a frequency shift in the harmonic spectra. The magnitude of the frequency shift depends on the orbiting speed of the hadron, which is considerable because the rotation period is in a few femtoseconds, a time scale that is comparable to that of infrared laser and is feasible in current laser experiments.

Passively mode-locked interband cascade optical frequency combs.

PubMed

Bagheri, Mahmood; Frez, Clifford; Sterczewski, Lukasz A; Gruidin, Ivan; Fradet, Mathieu; Vurgaftman, Igor; Canedy, Chadwick L; Bewley, William W; Merritt, Charles D; Kim, Chul Soo; Kim, Mijin; Meyer, Jerry R

2018-02-20

Since their inception, optical frequency combs have transformed a broad range of technical and scientific disciplines, spanning time keeping to navigation. Recently, dual comb spectroscopy has emerged as an attractive alternative to traditional Fourier transform spectroscopy, since it offers higher measurement sensitivity in a fraction of the time. Midwave infrared (mid-IR) frequency combs are especially promising as an effective means for probing the strong fundamental absorption lines of numerous chemical and biological agents. Mid-IR combs have been realized via frequency down-conversion of a near-IR comb, by optical pumping of a micro-resonator, and beyond 7 μm by four-wave mixing in a quantum cascade laser. In this work, we demonstrate an electrically-driven frequency comb source that spans more than 1 THz of bandwidth centered near 3.6 μm. This is achieved by passively mode-locking an interband cascade laser (ICL) with gain and saturable absorber sections monolithically integrated on the same chip. The new source will significantly enhance the capabilities of mid-IR multi-heterodyne frequency comb spectroscopy systems.

Intrinsic chirality and prochirality at Air/R-(+)- and S-(-)-limonene interfaces: spectral signatures with interference chiral sum-frequency generation vibrational spectroscopy.

PubMed

Fu, Li; Zhang, Yun; Wei, Zhe-Hao; Wang, Hong-Fei

2014-09-01

We report in this work detailed measurements of the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050 cm(-1)) of the air/liquid interfaces of R-(+)-limonene and S-(-)-limonene, using the recently developed high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The achiral SFG spectra of R-limonene and S-limonene, as well as the RS racemic mixture (50/50 equal amount mixture), show that the corresponding molecular groups of the R and S enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit a spectral signature from the chiral response of the Cα-H stretching mode, and a spectral signature from the prochiral response of the CH(2) asymmetric stretching mode, respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-(+)-limonene to S-(-)-limonene surfaces, and disappears for the RS racemic mixture surface. While the prochiral spectral feature of the CH(2) asymmetric stretching mode is the same for R-(+)-limonene and S-(-)-limonene surfaces, and also surprisingly remains the same for the RS racemic mixture surface. Therefore, the structures of the R-(+)-limonene and the S-(-)-limonene at the liquid interfaces are nevertheless not mirror images to each other, even though the corresponding groups have the same tilt angle from the interfacial normal, i.e., the R-(+)-limonene and the S-(-)-limonene at the surface are diastereomeric instead of enantiomeric. These results provide detailed information in understanding the structure and chirality of molecular interfaces and demonstrate the sensitivity and potential of SFG-VS as a unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface. © 2014 Wiley Periodicals, Inc.

Shell-isolated nanoparticle-enhanced Raman spectroscopy: principle and applications (Presentation Recording)

NASA Astrophysics Data System (ADS)

Li, Jian-Feng; Tian, Zhong-Qun

2015-08-01

Surface-enhanced Raman spectroscopy (SERS) is a powerful technique that yields fingerprint vibrational information with ultra-high sensitivity. However, only roughened Ag, Au and Cu surfaces can generate strong SERS effect. The lack of materials and morphology generality has severely limited the breadth of SERS practical applications on surface science, electrochemistry and catalysis. Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) was therefore invented to break the long-standing limitation of SERS. In SHINERS, Au@SiO2 core-shell nanoparticles were rationally designed. The gold core acts as plasmonic antenna and encapsulated by an ultra-thin, uniform and pinhole-free silica shell, can provide high electromagnetic field to enhance the Raman signals of probed molecules. The inert silica shell acts as tunneling barrier prevents the core from interacting with the environment. SHINERS has already been applied to a number of challenging systems, such as hydrogen and CO on Pt(hkl) and Rh(hkl), which can't be realized by traditional SERS. Combining with electrochemical methods, we has investigated the adsorption processes of pyridine at the Au(hkl) single crystal/solution interface, and in-situ monitored the surface electro-oxidation at Au(hkl) electrodes. These pioneering studies demonstrate convincingly the ability of SHINERS in exploring correlations between structure and reactivity as well as in monitoring intermediates at the interfaces. SHINERS was also explored from semiconductor surface for industry, to living bacteria for life science, and to pesticide residue detection for food safety. The concept of shell-isolated nanoparticle-enhancement is being applied to other spectroscopies such as infrared absorption, sum frequency generation and fluorescence. Jian-Feng Li et al., Nature, 2010, 464, 392-395.

Investigation of conduction and relaxation phenomena in BaZrxTi1-xO3 (x=0.05) by impedance spectroscopy

NASA Astrophysics Data System (ADS)

Mahajan, Sandeep; Haridas, Divya; Ali, S. T.; Munirathnam, N. R.; Sreenivas, K.; Thakur, O. P.; Prakash, Chandra

2014-10-01

In present study we have prepared ferroelectric BaZrxTi1-xO3 (x=0.05) ceramic by conventional solid state reaction route and studied its electrical properties as a function of temperature and frequency. X-ray diffraction (XRD) analysis shows single-phase formation of the compound with orthorhombic crystal structure at room temperature. Impedance and electric modulus spectroscopy analysis in the frequency range of 40 Hz-1 MHz at high temperature (200-600 °C) suggests two relaxation processes with different time constant are involved which are attributed to bulk and grain boundary effects. Frequency dependent dielectric plot at different temperature shows normal variation with frequency while dielectric loss (tanδ) peak was found to obey an Arrhenius law with activation energy of 1.02 eV. The frequency-dependent AC conductivity data were also analyzed in a wide temperature range. In present work we have studied the role of grain and grain boundaries on the electrical behaviour of Zr-doped BaTiO3 and their dependence on temperature and frequency by complex impedance and modulus spectroscopy (CIS) technique in a wide frequency (40 Hz-1 MHz) and high temperature range.

Delivering Microwave Spectroscopy to the Masses: a Design of a Low-Cost Microwave Spectrometer Operating in the 18-26 GHZ Frequency Range

NASA Astrophysics Data System (ADS)

Steber, Amanda; Pate, Brooks

2014-06-01

Advances in chip-level microwave technology in the communications field have led to the possibilities of low cost alternatives for current Fourier transform microwave (FTMW) spectrometers. Many of the large, expensive microwave components in a traditional design can now be replaced by robust, mass market monolithic microwave integrated circuits (MMICs). "Spectrometer on a board" designs are now feasible that offer dramatic cost reduction for microwave spectroscopy. These chip-level components can be paired with miniature computers to produce compact instruments that are operable through USB. A FTMW spectrometer design using the key MMIC components that drive cost reduction will be presented. Two dual channel synthesizers (Valon Technology Model 5008), a digital pattern generator (Byte Paradigm Wav Gen Xpress), and a high-speed digitizer/arbitrary waveform generator combination unit (Tie Pie HS-5 530 XM) form the key components of the spectrometer for operation in the 18-26.5 GHz range. The design performance is illustrated using a spectrometer that is being incorporated into a museum display for astrochemistry. For this instrument a user interface, developed in Python, has been developed and will be shown.

Non-thermal atmospheric pressure HF plasma source: generation of nitric oxide and ozone for bio-medical applications

NASA Astrophysics Data System (ADS)

Kühn, S.; Bibinov, N.; Gesche, R.; Awakowicz, P.

2010-01-01

A new miniature high-frequency (HF) plasma source intended for bio-medical applications is studied using nitrogen/oxygen mixture at atmospheric pressure. This plasma source can be used as an element of a plasma source array for applications in dermatology and surgery. Nitric oxide and ozone which are produced in this plasma source are well-known agents for proliferation of the cells, inhalation therapy for newborn infants, disinfection of wounds and blood ozonation. Using optical emission spectroscopy, microphotography and numerical simulation, the gas temperature in the active plasma region and plasma parameters (electron density and electron distribution function) are determined for varied nitrogen/oxygen flows. The influence of the gas flows on the plasma conditions is studied. Ozone and nitric oxide concentrations in the effluent of the plasma source are measured using absorption spectroscopy and electro-chemical NO-detector at variable gas flows. Correlations between plasma parameters and concentrations of the particles in the effluent of the plasma source are discussed. By varying the gas flows, the HF plasma source can be optimized for nitric oxide or ozone production. Maximum concentrations of 2750 ppm and 400 ppm of NO and O3, correspondingly, are generated.

Electromagnetic field enhancement and spectrum shaping through plasmonically integrated optical vortices.

PubMed

Ahn, Wonmi; Boriskina, Svetlana V; Hong, Yan; Reinhard, Björn M

2012-01-11

We introduce a new design approach for surface-enhanced Raman spectroscopy (SERS) substrates that is based on molding the optical powerflow through a sequence of coupled nanoscale optical vortices "pinned" to rationally designed plasmonic nanostructures, referred to as Vortex Nanogear Transmissions (VNTs). We fabricated VNTs composed of Au nanodiscs by electron beam lithography on quartz substrates and characterized their near- and far-field responses through combination of computational electromagnetism, and elastic and inelastic scattering spectroscopy. Pronounced dips in the far-field scattering spectra of VNTs provide experimental evidence for an efficient light trapping and circulation within the nanostructures. Furthermore, we demonstrate that VNT integration into periodic arrays of Au nanoparticles facilitates the generation of high E-field enhancements in the VNTs at multiple defined wavelengths. We show that spectrum shaping in nested VNT structures is achieved through an electromagnetic feed-mechanism driven by the coherent multiple scattering in the plasmonic arrays and that this process can be rationally controlled by tuning the array period. The ability to generate high E-field enhancements at predefined locations and frequencies makes nested VNTs interesting substrates for challenging SERS applications. © 2011 American Chemical Society

Difference frequency generation of Mid-IR radiation in PPLN crystals using a dual-wavelength all-fiber amplifier

NASA Astrophysics Data System (ADS)

Krzempek, Karol; Soboń, Grzegorz; Dudzik, Grzegorz; Sotor, Jaroslaw; Abramski, Krzysztof M.

2014-02-01

We present a method of generating mid-IR radiation by means of nonlinear difference frequency generation (DFG) effects occurring in periodically polled lithium niobate (PPLN) crystals using an all-fiber dual-wavelength amplifier. The presented mid-IR laser source incorporates an unique double-clad (DC) Erbium and Ytterbium (Er-Yb) doped amplifier stage capable of simultaneous amplification of both wavelengths required in the DFG process - 1064 nm and 1550 nm. The amplifier delivered more than 23.7 dB and 14.4 dB of amplification for 1550 nm and 1064 nm wavelength, low power, off-the-shelf, fiber pigtailed, distributed feedback (DFB) laser diodes, respectively. The dual-wavelength amplifier parameters crucial for the DFG process were investigated, including long-term power and polarization instabilities and optical spectrum characteristics of both amplified wavelengths. The DFG setup used a single collimator radiation delivery scheme and an 40 mm long MgO doped PPLN crystal. In effect the DFG source was capable of generating 1.14 mW of radiation centered around 3.4 μm. The overall performance of the mid-IR source was elaborated by performing sensitive Tunable Diode Laser Absorption Spectroscopy (TDLAS) detection of methane (CH4) in ambient air on an free-space optical path-length of 8 m. The measured detection limit of the sensor was 26 ppbv with a 1σ SNR of 69.

High-Performance Optical Frequency References for Space

NASA Astrophysics Data System (ADS)

Schuldt, Thilo; Döringshoff, Klaus; Milke, Alexander; Sanjuan, Josep; Gohlke, Martin; Kovalchuk, Evgeny V.; Gürlebeck, Norman; Peters, Achim; Braxmaier, Claus

2016-06-01

A variety of future space missions rely on the availability of high-performance optical clocks with applications in fundamental physics, geoscience, Earth observation and navigation and ranging. Examples are the gravitational wave detector eLISA (evolved Laser Interferometer Space Antenna), the Earth gravity mission NGGM (Next Generation Gravity Mission) and missions, dedicated to tests of Special Relativity, e.g. by performing a Kennedy- Thorndike experiment testing the boost dependence of the speed of light. In this context we developed optical frequency references based on Doppler-free spectroscopy of molecular iodine; compactness and mechanical and thermal stability are main design criteria. With a setup on engineering model (EM) level we demonstrated a frequency stability of about 2·10-14 at an integration time of 1 s and below 6·10-15 at integration times between 100s and 1000s, determined from a beat-note measurement with a cavity stabilized laser where a linear drift was removed from the data. A cavity-based frequency reference with focus on improved long-term frequency stability is currently under development. A specific sixfold thermal shield design based on analytical methods and numerical calculations is presented.

Frequency and time domain studies of magneto-transport and charge trapping in amorphous organic semiconductors

NASA Astrophysics Data System (ADS)

Rybicki, James Edward

The focus of this thesis is a recently discovered organic magnetoresistance (OMAR) whose underlying mechanism remains much debated. As an introduction, the field of organic electronic is briefly discussed focusing mainly on organic light emitting diodes, the devices in which OMAR was first discovered. Important findings related to OMAR from prior work are highlighted and several proposed models for the underlying mechanism are discussed. The frequency dependence of OMAR along with capacitance spectroscopy are studied to help distinguish between proposed models. The limit frequency for OMAR devices is obtained. Magnetic field dependent time-of-flight spectroscopy is used to determine whether applied magnetic fields modify the photocarrier generation efficiency in OMAR devices, their mobility, or both. These results are used to compare the bipolaron model and the triplet-polaron scattering mechanism. As it is generally agreed that OMAR is a spintronic effect, the role of spin-orbit coupling in polymers was studied to help understand its importance in the spin-transport of organic semiconductors. The possibility of spin-orbit induced spin precession is examined and a phonon assisted spin-flip process is proposed. We show OMAR may be enhanced by exposure to x-ray radiation. This is shown to be related to the production of traps. The effect on other device characteristics including turn-voltage and quantum efficiency is also examined. The role of trap production in enhancing OMAR is explained using the biopolaron model.

Forbidden atomic transitions driven by an intensity-modulated laser trap.

PubMed

Moore, Kaitlin R; Anderson, Sarah E; Raithel, Georg

2015-01-20

Spectroscopy is an essential tool in understanding and manipulating quantum systems, such as atoms and molecules. The model describing spectroscopy includes the multipole-field interaction, which leads to established spectroscopic selection rules, and an interaction that is quadratic in the field, which is not often employed. However, spectroscopy using the quadratic (ponderomotive) interaction promises two significant advantages over spectroscopy using the multipole-field interaction: flexible transition rules and vastly improved spatial addressability of the quantum system. Here we demonstrate ponderomotive spectroscopy by using optical-lattice-trapped Rydberg atoms, pulsating the lattice light and driving a microwave atomic transition that would otherwise be forbidden by established spectroscopic selection rules. This ability to measure frequencies of previously inaccessible transitions makes possible improved determinations of atomic characteristics and constants underlying physics. The spatial resolution of ponderomotive spectroscopy is orders of magnitude better than the transition frequency would suggest, promising single-site addressability in dense particle arrays for quantum computing applications.

Systematic errors in the determination of the spectroscopic g-factor in broadband ferromagnetic resonance spectroscopy: A proposed solution

NASA Astrophysics Data System (ADS)

Gonzalez-Fuentes, C.; Dumas, R. K.; García, C.

2018-01-01

A theoretical and experimental study of the influence of small offsets of the magnetic field (δH) on the measurement accuracy of the spectroscopic g-factor (g) and saturation magnetization (Ms) obtained by broadband ferromagnetic resonance (FMR) measurements is presented. The random nature of δH generates systematic and opposite sign deviations of the values of g and Ms with respect to their true values. A δH on the order of a few Oe leads to a ˜10% error of g and Ms for a typical range of frequencies employed in broadband FMR experiments. We propose a simple experimental methodology to significantly minimize the effect of δH on the fitted values of g and Ms, eliminating their apparent dependence in the range of frequencies employed. Our method was successfully tested using broadband FMR measurements on a 5 nm thick Ni80Fe20 film for frequencies ranging between 3 and 17 GHz.

Structure from Dynamics: Vibrational Dynamics of Interfacial Water as a Probe of Aqueous Heterogeneity

PubMed Central

2018-01-01

The structural heterogeneity of water at various interfaces can be revealed by time-resolved sum-frequency generation spectroscopy. The vibrational dynamics of the O–H stretch vibration of interfacial water can reflect structural variations. Specifically, the vibrational lifetime is typically found to increase with increasing frequency of the O–H stretch vibration, which can report on the hydrogen-bonding heterogeneity of water. We compare and contrast vibrational dynamics of water in contact with various surfaces, including vapor, biomolecules, and solid interfaces. The results reveal that variations in the vibrational lifetime with vibrational frequency are very typical, and can frequently be accounted for by the bulk-like heterogeneous response of interfacial water. Specific interfaces exist, however, for which the behavior is less straightforward. These insights into the heterogeneity of interfacial water thus obtained contribute to a better understanding of complex phenomena taking place at aqueous interfaces, such as photocatalytic reactions and protein folding. PMID:29490138

Solid-state dynamic nuclear polarization at 263 GHz: spectrometer design and experimental results†

PubMed Central

Rosay, Melanie; Tometich, Leo; Pawsey, Shane; Bader, Reto; Schauwecker, Robert; Blank, Monica; Borchard, Philipp M.; Cauffman, Stephen R.; Felch, Kevin L.; Weber, Ralph T.; Temkin, Richard J.; Griffin, Robert G.; Maas, Werner E.

2015-01-01

Dynamic Nuclear Polarization (DNP) experiments transfer polarization from electron spins to nuclear spins with microwave irradiation of the electron spins for enhanced sensitivity in nuclear magnetic resonance (NMR) spectroscopy. Design and testing of a spectrometer for magic angle spinning (MAS) DNP experiments at 263 GHz microwave frequency, 400 MHz 1H frequency is described. Microwaves are generated by a novel continuous-wave gyrotron, transmitted to the NMR probe via a transmission line, and irradiated on a 3.2 mm rotor for MAS DNP experiments. DNP signal enhancements of up to 80 have been measured at 95 K on urea and proline in water–glycerol with the biradical polarizing agent TOTAPOL. We characterize the experimental parameters affecting the DNP efficiency: the magnetic field dependence, temperature dependence and polarization build-up times, microwave power dependence, sample heating effects, and spinning frequency dependence of the DNP signal enhancement. Stable system operation, including DNP performance, is also demonstrated over a 36 h period. PMID:20449524

Femtosecond resolution of soft mode dynamics in structural phase transitions

NASA Technical Reports Server (NTRS)

Dougherty, Thomas P.; Wiederrecht, Gary P.; Nelson, Keith A.; Garrett, Mark H.; Jensen, Hans P.; Warde, Cardinal

1992-01-01

The microscopic pathway along which ions or molecules in a crystal move during structural phase transition can often be described in terms of a collective vibrational mode of the lattice. In many cases, this mode, called a 'soft' phonon mode because of its characteristically low frequency near the phase transition temperature, is difficult to characterize through conventional frequency-domain spectroscopies such as light or neutron scattering. A femtosecond time-domain analog of light-scattering spectroscopy called impulsive stimulated Raman scattering (ISRS) has been used to examine the soft modes of two perovskite ferroelectric crystals. The low-frequency lattice dynamics of KNbO3 and BaTiO3 are clarified in a manner that permits critical evaluation of microscopic models for their ferroelectric transitions. The results illustrate the advantages of ISRS over conventional Raman spectroscopy of low-frequency, heavily damped soft modes.

Precision Spectroscopy, Diode Lasers, and Optical Frequency Measurement Technology

NASA Technical Reports Server (NTRS)

Hollberg, Leo (Editor); Fox, Richard (Editor); Waltman, Steve (Editor); Robinson, Hugh

1998-01-01

This compilation is a selected set of reprints from the Optical Frequency Measurement Group of the Time and Frequency Division of the National Institute of Standards and Technology, and consists of work published between 1987 and 1997. The two main programs represented here are (1) development of tunable diode-laser technology for scientific applications and precision measurements, and (2) research toward the goal of realizing optical-frequency measurements and synthesis. The papers are organized chronologically in five, somewhat arbitrarily chosen categories: Diode Laser Technology, Tunable Laser Systems, Laser Spectroscopy, Optical Synthesis and Extended Wavelength Coverage, and Multi-Photon Interactions and Optical Coherences.

Polyvinylidene fluoride membranes probed by electrochemical impedance spectroscopy

NASA Astrophysics Data System (ADS)

Luo, Qi-Zhao; Huang, Qing; Chen, Zhe; Yao, Lei; Fu, Ping; Lin, Zhi-Dong

2018-06-01

Electrochemical impedance spectroscopy (EIS) has been applied to characterize the structure of polyvinylidene fluoride (PVDF) membranes. The characteristic frequency, which directly obtained from the original EIS data, was used to clarify the difference of the membranes’ structures. The experimental data indicated the equivalence between the characteristic frequency and the membrane resistance fitted from the equivalent circuit. The results evidenced that the characteristic frequency obtained directly from original EIS data without any fitting calculation can be used for in situ characterizing a membrane instead of the membrane resistance.

Mid-infrared wavelength- and frequency-modulation spectroscopy with a pump-modulated singly-resonant optical parametric oscillator

NASA Astrophysics Data System (ADS)

Lindsay, I. D.; Groß, P.; Lee, C. J.; Adhimoolam, B.; Boller, K.-J.

2006-12-01

We describe the implementation of the wavelength- and frequency-modulation spectroscopy techniques using a singly-resonant optical parametric oscillator (OPO) pumped by a fiber-amplified diode laser. Frequency modulation of the diode laser was transferred to the OPO’s mid-infrared idler output, avoiding the need for external modulation devices. This approach thus provides a means of implementing these important techniques with powerful, widely tunable, mid-infrared sources while retaining the simple, flexible modulation properties of diode lasers.

SFG characterization of a cationic ONLO dye in biological thin films

NASA Astrophysics Data System (ADS)

Johnson, Lewis E.; Casford, Michael T.; Elder, Delwin L.; Davies, Paul B.; Johal, Malkiat S.

2013-10-01

Biopolymer-based thin films, such as those composed of CTMA-DNA, can be used as a host material for NLOactive dyes for applications such as electro-optic (EO) switching and second harmonic generation. Previous work by Heckman et al. (Proc. SPIE 6401, 640108-2) has demonstrated functioning DNA-based EO modulators. Improved performance requires optimization of both the first hyperpolarizabilities (β) and degree of acentric ordering exhibited by the chromophores. The cationic dye DANPY-1 (Proc. SPIE 8464, 846409-D) has a high affinity for DNA and a substantial hyperpolarizability; however, its macroscopic ordering has not been previously characterized. We have characterized the acentric ordering of the dye using sum-frequency generation (SFG) vibrational spectroscopy in surface-immobilized DNA and on planar metal and dielectric surfaces.

Oxygen Plasma Modification of Poss-Coated Kapton(Registered TradeMark) HN Films

NASA Technical Reports Server (NTRS)

Wohl, C. J.; Belcher, M. A.; Ghose, S.; Connell, J. W.

2008-01-01

The surface energy of a material depends on both surface composition and topographic features. In an effort to modify the surface topography of Kapton(Registered TradeMark) HN film, organic solutions of a polyhedral oligomeric silsesquioxane, octakis(dimethylsilyloxy)silsesquioxane (POSS), were spray-coated onto the Kapton(Registered TradeMark) HN surface. Prior to POSS application, the Kapton(Registered TradeMark) HN film was activated by exposure to radio frequency (RF)-generated oxygen plasma. After POSS deposition and solvent evaporation, the films were exposed to various durations of RF-generated oxygen plasma to create a topographically rich surface. The modified films were characterized using optical microscopy, attenuated total reflection infrared (ATR-IR) spectroscopy, and high-resolution scanning electron microscopy (HRSEM). The physical properties of the modified films will be presented.

Accurate wavelengths for X-ray spectroscopy and the NIST hydrogen-like ion database

NASA Astrophysics Data System (ADS)

Kotochigova, S. A.; Kirby, K. P.; Brickhouse, N. S.; Mohr, P. J.; Tupitsyn, I. I.

2005-06-01

We have developed an ab initio multi-configuration Dirac-Fock-Sturm method for the precise calculation of X-ray emission spectra, including energies, transition wavelengths and transition probabilities. The calculations are based on non-orthogonal basis sets, generated by solving the Dirac-Fock and Dirac-Fock-Sturm equations. Inclusion of Sturm functions into the basis set provides an efficient description of correlation effects in highly charged ions and fast convergence of the configuration interaction procedure. A second part of our study is devoted to developing a theoretical procedure and creating an interactive database to generate energies and transition frequencies for hydrogen-like ions. This procedure is highly accurate and based on current knowledge of the relevant theory, which includes relativistic, quantum electrodynamic, recoil, and nuclear size effects.

Element Selectivity in Second-Harmonic Generation of GaFeO3 by a Soft-X-Ray Free-Electron Laser

NASA Astrophysics Data System (ADS)

Yamamoto, Sh.; Omi, T.; Akai, H.; Kubota, Y.; Takahashi, Y.; Suzuki, Y.; Hirata, Y.; Yamamoto, K.; Yukawa, R.; Horiba, K.; Yumoto, H.; Koyama, T.; Ohashi, H.; Owada, S.; Tono, K.; Yabashi, M.; Shigemasa, E.; Yamamoto, S.; Kotsugi, M.; Wadati, H.; Kumigashira, H.; Arima, T.; Shin, S.; Matsuda, I.

2018-06-01

Nonlinear optical frequency conversion has been challenged to move down to the extreme ultraviolet and x-ray region. However, the extremely low signals have allowed researchers to only perform transmission experiments of the gas phase or ultrathin films. Here, we report second harmonic generation (SHG) of the reflected beam of a soft x-ray free-electron laser from a solid, which is enhanced by the resonant effect. The observation revealed that the double resonance condition can be met by absorption edges for transition metal oxides in the soft x-ray range, and this suggests that the resonant SHG technique can be applicable to a wide range of materials. We discuss the possibility of element-selective SHG spectroscopy measurements in the soft x-ray range.

Offset-Free Gigahertz Midinfrared Frequency Comb Based on Optical Parametric Amplification in a Periodically Poled Lithium Niobate Waveguide

NASA Astrophysics Data System (ADS)

Mayer, A. S.; Phillips, C. R.; Langrock, C.; Klenner, A.; Johnson, A. R.; Luke, K.; Okawachi, Y.; Lipson, M.; Gaeta, A. L.; Fejer, M. M.; Keller, U.

2016-11-01

We report the generation of an optical-frequency comb in the midinfrared region with 1-GHz comb-line spacing and no offset with respect to absolute-zero frequency. This comb is tunable from 2.5 to 4.2 μ m and covers a critical spectral region for important environmental and industrial applications, such as molecular spectroscopy of trace gases. We obtain such a comb using a highly efficient frequency conversion of a near-infrared frequency comb. The latter is based on a compact diode-pumped semiconductor saturable absorber mirror-mode-locked ytterbium-doped calcium-aluminum gadolynate (Yb:CALGO) laser operating at 1 μ m . The frequency-conversion process is based on optical parametric amplification (OPA) in a periodically poled lithium niobate (PPLN) chip containing buried waveguides fabricated by reverse proton exchange. The laser with a repetition rate of 1 GHz is the only active element of the system. It provides the pump pulses for the OPA process as well as seed photons in the range of 1.4 - 1.8 μ m via supercontinuum generation in a silicon-nitride (Si3 N4 ) waveguide. Both the PPLN and Si3 N4 waveguides represent particularly suitable platforms for low-energy nonlinear interactions; they allow for mid-IR comb powers per comb line at the microwatt level and signal amplification levels up to 35 dB, with 2 orders of magnitude less pulse energy than reported in OPA systems using bulk devices. Based on numerical simulations, we explain how high amplification can be achieved at low energy using the interplay between mode confinement and a favorable group-velocity mismatch configuration where the mid-IR pulse moves at the same velocity as the pump.

Advancing the frontiers in nanocatalysis, biointerfaces, and renewable energy conversion by innovations of surface techniques.

PubMed

Somorjai, Gabor A; Frei, Heinz; Park, Jeong Y

2009-11-25

The challenge of chemistry in the 21st century is to achieve 100% selectivity of the desired product molecule in multipath reactions ("green chemistry") and develop renewable energy based processes. Surface chemistry and catalysis play key roles in this enterprise. Development of in situ surface techniques such as high-pressure scanning tunneling microscopy, sum frequency generation (SFG) vibrational spectroscopy, time-resolved Fourier transform infrared methods, and ambient pressure X-ray photoelectron spectroscopy enabled the rapid advancement of three fields: nanocatalysts, biointerfaces, and renewable energy conversion chemistry. In materials nanoscience, synthetic methods have been developed to produce monodisperse metal and oxide nanoparticles (NPs) in the 0.8-10 nm range with controlled shape, oxidation states, and composition; these NPs can be used as selective catalysts since chemical selectivity appears to be dependent on all of these experimental parameters. New spectroscopic and microscopic techniques have been developed that operate under reaction conditions and reveal the dynamic change of molecular structure of catalysts and adsorbed molecules as the reactions proceed with changes in reaction intermediates, catalyst composition, and oxidation states. SFG vibrational spectroscopy detects amino acids, peptides, and proteins adsorbed at hydrophobic and hydrophilic interfaces and monitors the change of surface structure and interactions with coadsorbed water. Exothermic reactions and photons generate hot electrons in metal NPs that may be utilized in chemical energy conversion. The photosplitting of water and carbon dioxide, an important research direction in renewable energy conversion, is discussed.

Back-surface gold mirrors for vibrationally resonant sum-frequency (VR-SFG) spectroscopy using 3-mercaptopropyltrimethoxysilane as an adhesion promoter.

PubMed

Quast, Arthur D; Zhang, Feng; Linford, Matthew R; Patterson, James E

2011-06-01

Back-surface mirrors are needed as reference materials for vibrationally resonant sum-frequency generation (VR-SFG) probing of liquid-solid interfaces. Conventional noble metal mirrors are not suitable for back-surface applications due to the presence of a metal adhesion layer (chromium or titanium) between the window substrate and the reflective metal surface. Using vapor deposited 3-mercaptopropyltrimethoxysilane (MPTMS) as a bi-functional adhesion promoter, gold mirrors were fabricated on fused silica substrates. These mirrors exhibit excellent gold adhesion as determined by the Scotch(®) tape test. They also produce minimal spectroscopic interference in the C-H stretching region (2800-3000 cm(-1)), as characterized by VR-SFG. These mirrors are thus robust and can be used as back-surface mirrors for a variety of applications, including reference mirrors for VR-SFG.

Iminopropadienones RN=C=C=C=O and bisiminopropadienes RN=C=C=C=NR: Matrix infrared spectra and anharmonic frequency calculations

NASA Astrophysics Data System (ADS)

Bégué, Didier; Baraille, Isabelle; Andersen, Heidi Gade; Wentrup, Curt

2013-10-01

Methyliminopropadienone MeN=C=C=C=O 1a was generated by flash vacuum thermolysis from four different precursors and isolated in solid argon. The matrix-isolation infrared spectrum is dominated by unusually strong anharmonic effects resulting in complex fine structure of the absorptions due to the NCCCO moiety in the 2200 cm-1 region. Doubling and tripling of the corresponding absorption bands are observed for phenyliminopropadienone PhN=C=C=C=O 1b and bis(phenylimino)propadiene PhN=C=C=C=NPh 9, respectively. Anharmonic vibrational frequency calculations allow the identification of a number of overtones and combination bands as the cause of the splittings for each molecule. This method constitutes an important tool for the characterization of reactive intermediates and unusual molecules by matrix-isolation infrared spectroscopy.

The structure of oleamide films at the aluminum/oil interface and aluminum/air interface studied by Sum Frequency Generation (SFG) vibrational spectroscopy and Reflection Absorption Infrared Spectroscopy (RAIRS).

PubMed

Casford, Michael T L; Davies, Paul B

2009-08-01

The structure of oleamide (cis-9-octadecenamide) films on aluminum has been investigated by sum frequency generation vibrational spectroscopy (SFG) and reflection absorption infrared spectroscopy (RAIRS). Three different film deposition strategies were investigated: (i) films formed by equilibrium adsorption from oleamide solutions in oil, (ii) Langmuir-Blodgett films cast at 1 and 25 mN m(-1), (iii) thick spin-cast films. Both L-B and spin-cast films were examined in air and under oil. The adsorbate formed in the 1 mN m(-1) film in air showed little orientational order. For this film, the spectroscopic results and the ellipsometric thickness point to a relatively conformationally disordered monolayer that is oriented principally in the plane of the interface. Direct adsorption to the metal interface from oil results in SFG spectra of oleamide that are comparable to those observed for the 1 mN m(-1) L-B film in air. In contrast, SFG and RAIRS results for the 25 mN m(-1) film in air and SFG spectra of the spin-cast film in air both show strong conformational ordering and orientational alignment normal to the interface. The 25 mN m(-1) film has an ellipsometric thickness almost twice that of the 1 mN m(-1) L-B film. Taken in combination with the spectroscopic results, this is indicative of a well packed monolayer in air in which the hydrocarbon chain is in an essentially defect-free extended conformation with the methyl terminus oriented away from the surface. A similar structure is also deduced for the surface of the spin-cast film in air. Upon immersion of the 25 mN m(-1) L-B film in oil the SFG spectra show that this film rapidly adopts a relatively disordered structure similar to that seen for the 1 mN m(-1) L-B film in air. Immersion of the spin-cast film in oil results in the gradual disordering of the amide film over a period of several days until the observed spectra become essentially identical to those observed for direct adsorption of oleamide from oil.

Sum Frequency Generation Vibrational Spectroscopy Studies on ModelPeptide Adsorption at the Hydrophobic Solid-Water and HydrophilicSolid-Water Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

York, Roger L.

2007-01-01

Sum frequency generation (SFG) vibrational spectroscopy has been used to study the interfacial structure of several polypeptides and amino acids adsorbed to hydrophobic and hydrophilic surfaces under a variety of experimental conditions. Peptide sequence, peptide chain length, peptide hydrophobicity, peptide side-chain type, surface hydrophobicity, and solution ionic strength all affect an adsorbed peptide's interfacial structure. Herein, it is demonstrated that with the choice of simple, model peptides and amino acids, surface specific SFG vibrational spectroscopy can be a powerful tool to elucidate the interfacial structure of these adsorbates. Herein, four experiments are described. In one, a series of isosequential amphiphilicmore » peptides are synthesized and studied when adsorbed to both hydrophobic and hydrophilic surfaces. On hydrophobic surfaces of deuterated polystyrene, it was determined that the hydrophobic part of the peptide is ordered at the solid-liquid interface, while the hydrophilic part of the peptide appears to have a random orientation at this interface. On a hydrophilic surface of silica, it was determined that an ordered peptide was only observed if a peptide had stable secondary structure in solution. In another experiment, the interfacial structure of a model amphiphilic peptide was studied as a function of the ionic strength of the solution, a parameter that could change the peptide's secondary structure in solution. It was determined that on a hydrophobic surface, the peptide's interfacial structure was independent of its structure in solution. This was in contrast to the adsorbed structure on a hydrophilic surface, where the peptide's interfacial structure showed a strong dependence on its solution secondary structure. In a third experiment, the SFG spectra of lysine and proline amino acids on both hydrophobic and hydrophilic surfaces were obtained by using a different experimental geometry that increases the SFG signal. Upon comparison of these spectra to the SFG spectra of interfacial polylysine and polyproline it was determined that the interfacial structure of a peptide is strongly dependent on its chain length. Lastly, SFG spectroscopy has been extended to the Amide I vibrational mode of a peptide (which is sensitive to peptide secondary structure) by building a new optical parametric amplifier based on lithium thioindate. Evidence is presented that suggests that the interfacial secondary structure of a peptide can be perturbed by a surface.« less

Probing the Orientation of Surface-Immobilized Protein G B1 Using ToF-SIMS Sum Frequency Generation and NEXAFS Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

L Baugh; T Weidner; J Baio

2011-12-31

The ability to orient active proteins on surfaces is a critical aspect of many medical technologies. An important related challenge is characterizing protein orientation in these surface films. This study uses a combination of time-of-flight secondary ion mass spectrometry (ToF-SIMS), sum frequency generation (SFG) vibrational spectroscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to characterize the orientation of surface-immobilized Protein G B1, a rigid 6 kDa domain that binds the Fc fragment of IgG. Two Protein G B1 variants with a single cysteine introduced at either end were immobilized via the cysteine thiol onto maleimide-oligo(ethylene glycol)-functionalized gold and baremore » gold substrates. X-ray photoelectron spectroscopy was used to measure the amount of immobilized protein, and ToF-SIMS was used to measure the amino acid composition of the exposed surface of the protein films and to confirm covalent attachment of protein thiol to the substrate maleimide groups. SFG and NEXAFS were used to characterize the ordering and orientation of peptide or side chain bonds. On both substrates and for both cysteine positions, ToF-SIMS data showed enrichment of mass peaks from amino acids located at the end of the protein opposite to the cysteine surface position as compared with nonspecifically immobilized protein, indicating end-on protein orientations. Orientation on the maleimide substrate was enhanced by increasing pH (7.0-9.5) and salt concentration (0-1.5 M NaCl). SFG spectral peaks characteristic of ordered {alpha}-helix and {beta}-sheet elements were observed for both variants but not for cysteine-free wild type protein on the maleimide surface. The phase of the {alpha}-helix and {beta}-sheet peaks indicated a predominantly upright orientation for both variants, consistent with an end-on protein binding configuration. Polarization dependence of the NEXAFS signal from the N 1s to {pi}* transition of {beta}-sheet peptide bonds also indicated protein ordering, with an estimated tilt angle of inner {beta}-strands of 40-50{sup o} for both variants (one variant more tilted than the other), consistent with SFG results. The combined results demonstrate the power of using complementary techniques to probe protein orientation on surfaces.« less

The molecular orientation of CO on Pd(1 1 1): a polarization-dependent SFG study

NASA Astrophysics Data System (ADS)

Galletto, Paolo; Unterhalt, Holger; Rupprechter, Günther

2003-01-01

The molecular orientation of carbon monoxide adsorbed on Pd(1 1 1) was examined by sum frequency generation (SFG) vibrational spectroscopy utilizing different polarization combinations of the visible and SFG light. This allows to determine the CO tilt angle with respect to the substrate, provided that a proper optical model for the interface can be defined. It is demonstrated that it is essential to invoke the βaac hyperpolarizability into the analysis and that polarization-dependent SFG of CO/Pd(1 1 1) yields information on βaac/ βccc rather than the tilt angle.

Determination of conformation and orientation of immobilized peptides and proteins at buried interfaces

NASA Astrophysics Data System (ADS)

Shen, Lei; Ulrich, Nathan W.; Mello, Charlene M.; Chen, Zhan

2015-01-01

Surface immobilized peptides/proteins have important applications such as antimicrobial coating and biosensing. We report a study of such peptides/proteins using sum frequency generation vibrational spectroscopy and ATR-FTIR. Immobilization on surfaces via physical adsorption and chemical coupling revealed that structures of chemically immobilized peptides are determined by immobilization sites, chemical environments, and substrate surfaces. In addition, controlling enzyme orientation by engineering the surface immobilization site demonstrated that structures can be well-correlated to measured chemical activity. This research facilitates the development of immobilized peptides/proteins with improved activities by optimizing their surface orientation and structure.

Microwave quantum logic gates for trapped ions.

PubMed

Ospelkaus, C; Warring, U; Colombe, Y; Brown, K R; Amini, J M; Leibfried, D; Wineland, D J

2011-08-10

Control over physical systems at the quantum level is important in fields as diverse as metrology, information processing, simulation and chemistry. For trapped atomic ions, the quantized motional and internal degrees of freedom can be coherently manipulated with laser light. Similar control is difficult to achieve with radio-frequency or microwave radiation: the essential coupling between internal degrees of freedom and motion requires significant field changes over the extent of the atoms' motion, but such changes are negligible at these frequencies for freely propagating fields. An exception is in the near field of microwave currents in structures smaller than the free-space wavelength, where stronger gradients can be generated. Here we first manipulate coherently (on timescales of 20 nanoseconds) the internal quantum states of ions held in a microfabricated trap. The controlling magnetic fields are generated by microwave currents in electrodes that are integrated into the trap structure. We also generate entanglement between the internal degrees of freedom of two atoms with a gate operation suitable for general quantum computation; the entangled state has a fidelity of 0.76(3), where the uncertainty denotes standard error of the mean. Our approach, which involves integrating the quantum control mechanism into the trapping device in a scalable manner, could be applied to quantum information processing, simulation and spectroscopy.

Tunability of the dielectric function of heavily doped germanium thin films for mid-infrared plasmonics

NASA Astrophysics Data System (ADS)

Frigerio, Jacopo; Ballabio, Andrea; Isella, Giovanni; Sakat, Emilie; Pellegrini, Giovanni; Biagioni, Paolo; Bollani, Monica; Napolitani, Enrico; Manganelli, Costanza; Virgilio, Michele; Grupp, Alexander; Fischer, Marco P.; Brida, Daniele; Gallacher, Kevin; Paul, Douglas J.; Baldassarre, Leonetta; Calvani, Paolo; Giliberti, Valeria; Nucara, Alessandro; Ortolani, Michele

2016-08-01

Heavily doped semiconductor thin films are very promising for application in mid-infrared plasmonic devices because the real part of their dielectric function is negative and broadly tunable in the 5 to 50 μ m wavelength range at least. In this work, we investigate the electrodynamics of heavily n -type-doped germanium epilayers at infrared frequencies beyond the assumptions of the Drude model. The films are grown on silicon and germanium substrates, are in situ doped with phosphorous in the 1017 to 1019 cm-3 range, then screened plasma frequencies in the 100 to 1200 cm-1 range were observed. We employ infrared spectroscopy, pump-probe spectroscopy, and dc transport measurements to determine the tunability of the plasma frequency. Although no plasmonic structures have been realized in this work, we derive estimates of the decay time of mid-infrared plasmons and of their figures of merit for field confinement and for surface plasmon propagation. The average electron scattering rate increases almost linearly with excitation frequency, in agreement with quantum calculations based on a model of the ellipsoidal Fermi surface at the conduction band minimum of germanium accounting for electron scattering with optical phonons and charged impurities. Instead, we found weak dependence of plasmon losses on neutral impurity density. In films where a transient plasma was generated by optical pumping, we found significant dependence of the energy relaxation times in the few-picosecond range on the static doping level of the film, confirming the key but indirect role played by charged impurities in energy relaxation. Our results indicate that underdamped mid-infrared plasma oscillations are attained in n -type-doped germanium at room temperature.

All-fiber mode-locked erbium-doped ring laser based on a highly-nonlinear resonator with a low-noise ultrashort pulse generation

NASA Astrophysics Data System (ADS)

Kudelin, Igor S.; Dvoretskiy, Dmitriy A.; Sazonkin, Stanislav G.; Orekhov, Ilya O.; Pnev, Alexey B.; Karasik, Valeriy E.; Denisov, Lev K.

2018-04-01

Ultrashort pulse (USP) fiber lasers have found applications in such various fields as frequency metrology and spectroscopy, telecommunication systems, etc. For the last decade, mode-locking (ML) fiber lasers have been under carefully investigations for scientific, medical and industrial applications. Also, USP fiber sources can be treated as an ideal platform to expand future applications due to the complex ML nonlinear dynamics with a presence of high value of group velocity dispersion (GVD) and the third order dispersion in the resonator. For more reliable and robust launching of passive mode-locking based on a nonlinear polarization evolution, we used a highly nonlinear germanosilicate fiber (with germanium oxides concentration in the core 50 mol. %) inside the cavity and we have obtained ultrashort stretched pulses with a high peak power and energy. In this work relative intensity noise and frequency repetition stability is improved by applying isolator-polarizer (ISO-PM) with increased extinction ratio Pext and by compensation of intracavity group-velocity dispersion from the value β2 - 0.021 ps2 to - 0.0053 ps2 at 1550 nm. As a result, we have obtained the low-noise stretched pulse generation with duration 180 fs at a repetition rate 11.3 MHz (with signal-tonoise ratio at fundamental frequency 59 dB) with Allan deviation of a pulse repetition frequency for 1 s interval 5,7 * 10-9 and a relative intensity noise < -101 dBc / Hz.

The Dawn of Ultrafast Nonlinear Optics in the Terahertz Regime

NASA Astrophysics Data System (ADS)

Blanchard, F.; Razzari, L.; Su, F. H.; Sharma, G.; Morandotti, Roberto; Ozaki, T.; Reid, M.; Hegmann, F. A.

The terahertz (THz) frequency range is a specific region of the electromagnetic spectrum also known as the far-infrared (FIR) region. More precisely, THz waves cover the region from 100 GHz to 20 THz, thus bridging the gap between microwaves and infrared light. Physically, 1 THz is equivalent to a wavelength of 300 μm in vacuum, to 33.3 cm-1 in terms of wave numbers, to a photon energy of 4 meV, or to a temperature of 48 K. THz waves have the ability to penetrate various materials including non-metallic compounds (papers and plastics), organics, gases, and liquids, thus being a powerful tool for spectroscopic sensing [1]. This portion of the electromagnetic spectrum has been accessible for some time by various means including molecular gas lasers, gyrotrons, and free-electron lasers [2]. Due to complexity, cost, and limited frequencies of operation, these sources have traditionally made it difficult to gain full access to the terahertz frequency range. Nevertheless, there were several pioneering works in nonlinear FIR spectroscopy already in the early 1970s, about one decade after the advent of the laser (readers may find a review in [3]). In particular, saturated absorption in the FIR region was first studied in 1970, which led to the optically pumped FIR gas laser [4]. In the 1980s, the first demonstration of THz radiation coherently generated and detected was made. This result coincided with the development of ultrafast lasers and was obtained using a photoconductive antenna emitter [5], where photoexcited carriers induced by an ultrafast laser pulse are accelerated by a biasing electric field. The resulting time varying current J(t) radiates an electromagnetic transient, E ∝ partial J/partial t , whose amplitude and phase depend on various parameters such as carrier mobility, carrier lifetime, bias field, and on the impurity doping concentration [6]. This allowed the birth of coherent time-domain THz spectroscopy (TDTS) [1], which provided unprecedented insights into the nature of molecular vibrations, carrier dynamics in semiconductors, and protein kinetics [7-12]. Even with 30 years of rapid advances in the study of light-matter interactions at THz frequencies, lack of efficient emitters and sensitive detectors in this frequency range has for long time slowed down THz linear and nonlinear spectroscopy.

Noise in NC-AFM measurements with significant tip–sample interaction

PubMed Central

Lübbe, Jannis; Temmen, Matthias

2016-01-01

The frequency shift noise in non-contact atomic force microscopy (NC-AFM) imaging and spectroscopy consists of thermal noise and detection system noise with an additional contribution from amplitude noise if there are significant tip–sample interactions. The total noise power spectral density D Δ f(f m) is, however, not just the sum of these noise contributions. Instead its magnitude and spectral characteristics are determined by the strongly non-linear tip–sample interaction, by the coupling between the amplitude and tip–sample distance control loops of the NC-AFM system as well as by the characteristics of the phase locked loop (PLL) detector used for frequency demodulation. Here, we measure D Δ f(f m) for various NC-AFM parameter settings representing realistic measurement conditions and compare experimental data to simulations based on a model of the NC-AFM system that includes the tip–sample interaction. The good agreement between predicted and measured noise spectra confirms that the model covers the relevant noise contributions and interactions. Results yield a general understanding of noise generation and propagation in the NC-AFM and provide a quantitative prediction of noise for given experimental parameters. We derive strategies for noise-optimised imaging and spectroscopy and outline a full optimisation procedure for the instrumentation and control loops. PMID:28144538

IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively.

PubMed

Ni, Yicun; Skinner, J L

2015-07-07

Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFG spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm(-1) and a positive band centered at 1670 cm(-1). We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.

IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively

NASA Astrophysics Data System (ADS)

Ni, Yicun; Skinner, J. L.

2015-07-01

Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFG spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm-1 and a positive band centered at 1670 cm-1. We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.

Do radio frequencies of medical instruments common in the operating room interfere with near-infrared spectroscopy signals?

NASA Astrophysics Data System (ADS)

Shadgan, Babak; Molavi, Behnam; Reid, W. D.; Dumont, Guy; Macnab, Andrew J.

2010-02-01

Background: Medical and diagnostic applications of near infrared spectroscopy (NIRS) are increasing, especially in operating rooms (OR). Since NIRS is an optical technique, radio frequency (RF) interference from other instruments is unlikely to affect the raw optical data, however, NIRS data processing and signal output could be affected. Methods: We investigated the potential for three common OR instruments: an electrical cautery, an orthopaedic drill and an imaging system, to generate electromagnetic interference (EMI) that could potentially influence NIRS signals. The time of onset and duration of every operation of each device was recorded during surgery. To remove the effects of slow changing physiological variables, we first used a lowpass filter and then selected 2 windows with variable lengths around the moment of device onset. For each instant, variances (energy) and means of the signals in the 2 windows were compared. Results: Twenty patients were studied during ankle surgery. Analysis shows no statistically significant difference in the means and variance of the NIRS signals (p < 0.01) during operation of any of the three devices for all surgeries. Conclusion: This method confirms the instruments evaluated caused no significant interference. NIRS can potentially be used without EMI in clinical environments such as the OR.

IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ni, Yicun; Skinner, J. L.

Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFGmore » spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm{sup −1} and a positive band centered at 1670 cm{sup −1}. We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.« less

Noise in NC-AFM measurements with significant tip-sample interaction.

PubMed

Lübbe, Jannis; Temmen, Matthias; Rahe, Philipp; Reichling, Michael

2016-01-01

The frequency shift noise in non-contact atomic force microscopy (NC-AFM) imaging and spectroscopy consists of thermal noise and detection system noise with an additional contribution from amplitude noise if there are significant tip-sample interactions. The total noise power spectral density D Δ f ( f m ) is, however, not just the sum of these noise contributions. Instead its magnitude and spectral characteristics are determined by the strongly non-linear tip-sample interaction, by the coupling between the amplitude and tip-sample distance control loops of the NC-AFM system as well as by the characteristics of the phase locked loop (PLL) detector used for frequency demodulation. Here, we measure D Δ f ( f m ) for various NC-AFM parameter settings representing realistic measurement conditions and compare experimental data to simulations based on a model of the NC-AFM system that includes the tip-sample interaction. The good agreement between predicted and measured noise spectra confirms that the model covers the relevant noise contributions and interactions. Results yield a general understanding of noise generation and propagation in the NC-AFM and provide a quantitative prediction of noise for given experimental parameters. We derive strategies for noise-optimised imaging and spectroscopy and outline a full optimisation procedure for the instrumentation and control loops.

Frequency divide-and-conquer approach to producing octave-wide frequency combs and few-cycle pulses in the mid-IR

NASA Astrophysics Data System (ADS)

Vodopyanov, Konstantin

2014-05-01

I will present a new technique for extending frequency combs to the highly desirable yet difficult-to-achieve mid-IR spectral range. The technique is based on subharmonic optical parametric oscillation (OPO) that can be considered as a reverse of the second harmonic generation process. The frequency comb of a pump laser is transposed to half of its central frequency and simultaneously spectrally augmented, thanks to an enormous gain bandwidth of the OPO near degeneracy, as well as due to massive cross-coupling between the laser and the OPO frequency comb components. Using ultrafast erbium (1.56 microns) or thulium (2 microns)-based fiber lasers as a pump and using thin, sub-mm-long, quasi phase-matched lithium niobate or gallium arsenide crystals, we produce frequency combs centered correspondingly at 3.1 or 4 micron subharmonic of the pump frequency. With the properly managed OPO cavity group velocity dispersion, octave-wide frequency combs spanning 2.5 - 6 micron range were achieved. Due to the doubly-resonant operation, the threshold of such a system is low (typically 10 mW) and by several experiments including measuring frequency beats between the OPO comb teeth and a narrow-linewidth CW laser and by interfering the outputs of two identical but distinct OPOs pumped by the same laser, we established that the frequency comb from a subharmonic OPO is phase-locked to that of the pump laser. Pulse duration measurements show that for the optimal intracavity dispersion conditions, we generate sub 5-cycle pulses at the subharmonic of the pump. I will also talk about applications of our mid-IR frequency combs to trace gas detection, where part-per-billion sensitivity of molecular detection is achieved as well as about Fourier spectroscopy using a dual-comb system consisting of two phase-locked lasers. I thank NASA, Office of Naval Research, Air Force Office of Scientific Research, Agilent Technologies, Sanofi- Aventis, Stanford University Bio-X, Stanford Medical School, and Stanford Woods Institute for their financial support.

Novel Cavities in Vertical External Cavity Surface Emitting Lasers for Emission in Broad Spectral Region by Means of Nonlinear Frequency Conversion

NASA Astrophysics Data System (ADS)

Lukowski, Michal L.

Optically pumped semiconductor vertical external cavity surface emitting lasers (VECSEL) were first demonstrated in the mid 1990's. Due to the unique design properties of extended cavity lasers VECSELs have been able to provide tunable, high-output powers while maintaining excellent beam quality. These features offer a wide range of possible applications in areas such as medicine, spectroscopy, defense, imaging, communications and entertainment. Nowadays, newly developed VECSELs, cover the spectral regions from red (600 nm) to around 5 microm. By taking the advantage of the open cavity design, the emission can be further expanded to UV or THz regions by the means of intracavity nonlinear frequency generation. The objective of this dissertation is to investigate and extend the capabilities of high-power VECSELs by utilizing novel nonlinear conversion techniques. Optically pumped VECSELs based on GaAs semiconductor heterostructures have been demonstrated to provide exceptionally high output powers covering the 900 to 1200 nm spectral region with diffraction limited beam quality. The free space cavity design allows for access to the high intracavity circulating powers where high efficiency nonlinear frequency conversions and wavelength tuning can be obtained. As an introduction, this dissertation consists of a brief history of the development of VECSELs as well as wafer design, chip fabrication and resonator cavity design for optimal frequency conversion. Specifically, the different types of laser cavities such as: linear cavity, V-shaped cavity and patented T-shaped cavity are described, since their optimization is crucial for transverse mode quality, stability, tunability and efficient frequency conversion. All types of nonlinear conversions such as second harmonic, sum frequency and difference frequency generation are discussed in extensive detail. The theoretical simulation and the development of the high-power, tunable blue and green VECSEL by the means of type I second harmonic generation in a V- cavity is presented. Tens of watts of output power for both blue and green wavelengths prove the viability for VECSELs to replace the other types of lasers currently used for applications in laser light shows, for Ti:Sapphire pumping, and for medical applications such as laser skin resurfacing. The novel, recently patented, two-chip T-cavity configuration allowing for spatial overlap of two, separate VECSEL cavities is described in detail. This type of setup is further used to demonstrate type II sum frequency generation to green with multi-watt output, and the full potential of the T-cavity is utilized by achieving type II difference frequency generation to the mid-IR spectral region. The tunable output around 5.4 microm with over 10 mW power is showcased. In the same manner the first attempts to generate THz radiation are discussed. Finally, a slightly modified T-cavity VECSEL is used to reach the UV spectral regions thanks to type I fourth harmonic generation. Over 100 mW at around 265 nm is obtained in a setup which utilizes no stabilization techniques. The dissertation demonstrates the flexibility of the VECSEL in achieving broad spectral coverage and thus its potential for a wide range of applications.

Transient ultrafast coherent spectroscopy of 2-propanol

NASA Astrophysics Data System (ADS)

Meiselman, Seth; Decamp, Matthew; Lorenz, Virginia

We use transient coherent spontaneous Raman spectroscopy to measure the coherence lifetimes of vibrational states in liquid propanol. By creating single-photon-level collective excitations of the vibrational states in the system we observe coherence oscillations due to simultaneous excitation of the 2885 cm-1, 2938 cm-1, and 2976 cm-1 modes. These lifetimes and oscillation frequencies agree with frequency-domain lineshape measurements.

Determination and Comparison of Carbonyl Stretching Frequency of a Ketone in Its Ground State and the First Electronic Excited State

ERIC Educational Resources Information Center

Bandyopadhyay, Subhajit; Roy, Saswata

2014-01-01

This paper describes an inexpensive experiment to determine the carbonyl stretching frequency of an organic keto compound in its ground state and first electronic excited state. The experiment is simple to execute, clarifies some of the fundamental concepts of spectroscopy, and is appropriate for a basic spectroscopy laboratory course. The…

Frequency shifts in gravitational resonance spectroscopy

DOE PAGES

Baeßler, S.; Nesvizhevsky, V. V.; Pignol, G.; ...

2015-02-25

Quantum states of ultracold neutrons in a gravitational field are characterized through gravitational resonance spectroscopy. This paper discusses systematic effects that appear in the spectroscopic measurements. The discussed frequency shifts-which we call the Stern-Gerlach shift, interference shift, and spectator-state shift-appear in conceivable measurement schemes and have general importance. Lastly, these shifts have to be taken into account in precision experiments.

Measurement of the 4 S1 /2→6 S1 /2 transition frequency in atomic potassium via direct frequency-comb spectroscopy

NASA Astrophysics Data System (ADS)

Stalnaker, J. E.; Ayer, H. M. G.; Baron, J. H.; Nuñez, A.; Rowan, M. E.

2017-07-01

We present an experimental determination of the 4 S1 /2→6 S1 /2 transition frequency in atomic potassium 39K, using direct frequency-comb spectroscopy. The output of a stabilized optical frequency comb was used to excite a thermal atomic vapor. The repetition rate of the frequency comb was scanned and the transitions were excited using stepwise two-photon excitation. The center-of-gravity frequency for the transition was found to be νcog=822 951 698.09 (13 ) MHz and the measured hyperfine A coefficient of the 6 S1 /2 state was 21.93 (11 ) MHz. The measurements are in agreement with previous values and represent an improvement by a factor of 700 in the uncertainty of the center-of-gravity measurement.

New Approach to Ultrasonic Spectroscopy Applied to Flywheel Rotors

NASA Technical Reports Server (NTRS)

Harmon, Laura M.; Baaklini, George Y.

2002-01-01

Flywheel energy storage devices comprising multilayered composite rotor systems are being studied extensively for use in the International Space Station. A flywheel system includes the components necessary to store and discharge energy in a rotating mass. The rotor is the complete rotating assembly portion of the flywheel, which is composed primarily of a metallic hub and a composite rim. The rim may contain several concentric composite rings. This article summarizes current ultrasonic spectroscopy research of such composite rings and rims and a flat coupon, which was manufactured to mimic the manufacturing of the rings. Ultrasonic spectroscopy is a nondestructive evaluation (NDE) method for material characterization and defect detection. In the past, a wide bandwidth frequency spectrum created from a narrow ultrasonic signal was analyzed for amplitude and frequency changes. Tucker developed and patented a new approach to ultrasonic spectroscopy. The ultrasonic system employs a continuous swept-sine waveform and performs a fast Fourier transform on the frequency spectrum to create the spectrum resonance spacing domain, or fundamental resonant frequency. Ultrasonic responses from composite flywheel components were analyzed at Glenn to assess this NDE technique for the quality assurance of flywheel applications.

Physiological denoising of BOLD fMRI data using Regressor Interpolation at Progressive Time Delays (RIPTiDe) processing of concurrent fMRI and near-infrared spectroscopy (NIRS).

PubMed

Frederick, Blaise deB; Nickerson, Lisa D; Tong, Yunjie

2012-04-15

Confounding noise in BOLD fMRI data arises primarily from fluctuations in blood flow and oxygenation due to cardiac and respiratory effects, spontaneous low frequency oscillations (LFO) in arterial pressure, and non-task related neural activity. Cardiac noise is particularly problematic, as the low sampling frequency of BOLD fMRI ensures that these effects are aliased in recorded data. Various methods have been proposed to estimate the noise signal through measurement and transformation of the cardiac and respiratory waveforms (e.g. RETROICOR and respiration volume per time (RVT)) and model-free estimation of noise variance through examination of spatial and temporal patterns. We have previously demonstrated that by applying a voxel-specific time delay to concurrently acquired near infrared spectroscopy (NIRS) data, we can generate regressors that reflect systemic blood flow and oxygenation fluctuations effects. Here, we apply this method to the task of removing physiological noise from BOLD data. We compare the efficacy of noise removal using various sets of noise regressors generated from NIRS data, and also compare the noise removal to RETROICOR+RVT. We compare the results of resting state analyses using the original and noise filtered data, and we evaluate the bias for the different noise filtration methods by computing null distributions from the resting data and comparing them with the expected theoretical distributions. Using the best set of processing choices, six NIRS-generated regressors with voxel-specific time delays explain a median of 10.5% of the variance throughout the brain, with the highest reductions being seen in gray matter. By comparison, the nine RETROICOR+RVT regressors together explain a median of 6.8% of the variance in the BOLD data. Detection of resting state networks was enhanced with NIRS denoising, and there were no appreciable differences in the bias of the different techniques. Physiological noise regressors generated using Regressor Interpolation at Progressive Time Delays (RIPTiDe) offer an effective method for efficiently removing hemodynamic noise from BOLD data. Copyright © 2012 Elsevier Inc. All rights reserved.

The effect of milling frequency on a mechanochemical organic reaction monitored by in situ Raman spectroscopy

PubMed Central

Julien, Patrick A; Malvestiti, Ivani

2017-01-01

We provide the first in situ and real-time study of the effect of milling frequency on the course of a mechanochemical organic reaction conducted using a vibratory shaker (mixer) ball mill. The use of in situ Raman spectroscopy for real-time monitoring of the mechanochemical synthesis of a 2,3-diphenylquinoxaline derivative revealed a pronounced dependence of chemical reactivity on small variations in milling frequency. In particular, in situ measurements revealed the establishment of two different regimes of reaction kinetics at different frequencies, providing tentative insight into processes of mechanical activation in organic mechanochemical synthesis. PMID:29114323

Frequency Dependence of Low-Voltage Electrowetting Investigated by Impedance Spectroscopy.

PubMed

Li, Ying-Jia; Cahill, Brian P

2017-11-14

An electrowetting-on-dielectric (EWOD) electrode was developed that facilitates the use of low alternating voltages (≤5 V AC ). This allows online investigation of the frequency dependence of electrowetting by means of impedance spectroscopy. The EWOD electrode is based on a dielectric bilayer consisting of an anodic tantalum pentoxide (Ta 2 O 5 ) thin film (d = 59.35 nm) with a high relative permittivity (ε d = 26.3) and a self-assembled hydrophobic silane monolayer. The frequency dependence of electrowetting was studied using an aqueous μL-sized sessile droplet on the planar EWOD electrode in oil. Experiments using electrochemical impedance spectroscopy and optical imaging indicate the frequency dependence of all three variables in the Young-Lippmann equation: the voltage drop across the dielectric layers, capacitance per unit area, and contact angle under voltage. The electrowetting behavior induced by AC voltages is shown to be well described by the Young-Lippmann equation for AC applications below a frequency threshold. Moreover, the dielectric layers act as a capacitor and the stored electrostatic potential energy is revealed to only partially contribute to the electrowetting.

Multi-Photon Micro-Spectroscopy of Biological Specimens

DTIC Science & Technology

2000-07-01

Micro-spectroscopy, multi-photon fluorescence spectroscopy, second harmonic generation, plant tissues, stem, chloroplast, protoplast, maize, Arabidopsis...harmonic generation (SHG) in the plant cell 5wall. In this case, micro-spectroscopy provides a means of verification that, indeed, SHG occurs in plant ...fluorescence microscopy -the response of plant cells to high intensity illumination," Micron (in press) 2000. 3. H.-C. Huang and C. -C Chen, "Genome

Generation of isolated attosecond pulses with enhancement cavities—a theoretical study

NASA Astrophysics Data System (ADS)

Högner, M.; Tosa, V.; Pupeza, I.

2017-03-01

The generation of extreme-ultraviolet (XUV) isolated attosecond pulses (IAPs) has enabled experimental access to the fastest phenomena in nature observed so far, namely the dynamics of electrons in atoms, molecules and solids. However, nowadays the highest repetition rates at which IAPs can be generated lies in the {kHz} range. This represents a rather severe restriction for numerous experiments involving the detection of charged particles, where the desired number of generated particles per shot is limited by space charge effects to ideally one. Here, we present a theoretical study on the possibility of efficiently producing IAPs at multi-{MHz} repetition rates via cavity-enhanced high-harmonic generation (HHG). To this end, we assume parameters of state-of-the-art Yb-based femtosecond laser technology to evaluate several time-gating methods which could generate IAPs in enhancement cavities. We identify polarization gating and a new method, employing non-collinear optical gating in a tailored transverse cavity mode, as suitable candidates and analyze these via extensive numerical modeling. The latter, which we dub transverse mode gating (TMG) promises the highest efficiency and robustness. Assuming 0.7 μ {{J}}, 5-cycle pulses from the seeding laser and a state-of-the-art enhancement cavity, we show that TMG bares the potential to generate IAPs with photon energies around 100 {eV} and a photon flux of at least {10}8 {photons} {{{s}}}-1 at repetition rates of 10 {MHz} and higher. This result reveals a roadmap towards a dramatic decrease in measurement time (and, equivalently, an increase in the signal-to-noise ratio) in photoelectron spectroscopy and microscopy. In particular, it paves the way to combining attosecond streaking with photoelectron emission microscopy, affording, for the first time, the spatially and temporally resolved observation of plasmonic fields in nanostructures. Furthermore, it promises the generation of frequency combs with an unprecedented bandwidth for XUV precision spectroscopy.

Gas spectroscopy with integrated frequency monitoring through self-mixing in a terahertz quantum-cascade laser.

PubMed

Chhantyal-Pun, Rabi; Valavanis, Alexander; Keeley, James T; Rubino, Pierluigi; Kundu, Iman; Han, Yingjun; Dean, Paul; Li, Lianhe; Davies, A Giles; Linfield, Edmund H

2018-05-15

We demonstrate a gas spectroscopy technique, using self-mixing in a 3.4 terahertz quantum-cascade laser (QCL). All previous QCL spectroscopy techniques have required additional terahertz instrumentation (detectors, mixers, or spectrometers) for system pre-calibration or spectral analysis. By contrast, our system self-calibrates the laser frequency (i.e., with no external instrumentation) to a precision of 630 MHz (0.02%) by analyzing QCL voltage perturbations in response to optical feedback within a 0-800 mm round-trip delay line. We demonstrate methanol spectroscopy by introducing a gas cell into the feedback path and show that a limiting absorption coefficient of ∼1×10 -4   cm -1 is resolvable.

Frequency Correction for MIRO Chirp Transformation Spectroscopy Spectrum

NASA Technical Reports Server (NTRS)

Lee, Seungwon

2012-01-01

This software processes the flyby spectra of the Chirp Transform Spectrometer (CTS) of the Microwave Instrument for Rosetta Orbiter (MIRO). The tool corrects the effect of Doppler shift and local-oscillator (LO) frequency shift during the flyby mode of MIRO operations. The frequency correction for CTS flyby spectra is performed and is integrated with multiple spectra into a high signal-to-noise averaged spectrum at the rest-frame RF frequency. This innovation also generates the 8 molecular line spectra by dividing continuous 4,096-channel CTS spectra. The 8 line spectra can then be readily used for scientific investigations. A spectral line that is at its rest frequency in the frame of the Earth or an asteroid will be observed with a time-varying Doppler shift as seen by MIRO. The frequency shift is toward the higher RF frequencies on approach, and toward lower RF frequencies on departure. The magnitude of the shift depends on the flyby velocity. The result of time-varying Doppler shift is that of an observed spectral line will be seen to move from channel to channel in the CTS spectrometer. The direction (higher or lower frequency) in the spectrometer depends on the spectral line frequency under consideration. In order to analyze the flyby spectra, two steps are required. First, individual spectra must be corrected for the Doppler shift so that individual spectra can be superimposed at the same rest frequency for integration purposes. Second, a correction needs to be applied to the CTS spectra to account for the LO frequency shifts that are applied to asteroid mode.

Reorientation of the ‘free OH’ group in the top-most layer of air/water interface of sodium fluoride aqueous solution probed with sum-frequency generation vibrational spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Ran-Ran; Guo, Yuan; Wang, Hongfei

2014-09-17

Many experimental and theoretical studies have established the specific anion, as well as cation effects on the hydrogen-bond structures at the air/water interface of electrolyte solutions. However, the ion effects on the top-most layer of the air/water interface, which is signified by the non-hydrogen-bonded so-called ‘free O-H’ group, has not been discussed or studied. In this report, we present the measurement of changes of the orientational angle of the ‘free O-H’ group at the air/water interface of the sodium fluoride (NaF) solutions at different concentrations using the interface selective sum-frequency generation vibrational spectroscopy (SFG-VS) in the ssp and ppp polarizations.more » The polarization dependent SFG-VS results show that the average tilt angle of the ‘free O-H’ changes from about 35.3 degrees ± 0.5 degrees to 43.4 degrees ± 2.1degrees as the NaF concentration increase from 0 to 0.94M (nearly saturated). Such tilt angle change is around the axis of the other O-H group of the same water molecule at the top-most layer at the air/water interface that is hydrogen-bonded to the water molecules below the top-most layer. These results provide quantitative molecular details of the ion effects of the NaF salt on the structure of the water molecules at the top-most layer of the air/water interfacial, even though both the Na+ cation and the F- anion are believed to be among the most excluded ions from the air/water interface.« less

Surface and buried interfacial structures of epoxy resins used as underfills studied by sum frequency generation vibrational spectroscopy.

PubMed

Vázquez, Anne V; Holden, Brad; Kristalyn, Cornelius; Fuller, Mike; Wilkerson, Brett; Chen, Zhan

2011-05-01

Flip chip technology has greatly improved the performance of semiconductor devices, but relies heavily on the performance of epoxy underfill adhesives. Because epoxy underfills are cured in situ in flip chip semiconductor devices, understanding their surface and interfacial structures is critical for understanding their adhesion to various substrates. Here, sum frequency generation (SFG) vibrational spectroscopy was used to study surface and buried interfacial structures of two model epoxy resins used as underfills in flip chip devices, bisphenol A digylcidyl ether (BADGE) and 1,4-butanediol diglycidyl ether (BDDGE). The surface structures of these epoxies were compared before and after cure, and the orientations of their surface functional groups were deduced to understand how surface structural changes during cure may affect adhesion properties. Further, the effect of moisture exposure, a known cause of adhesion failure, on surface structures was studied. It was found that the BADGE surface significantly restructured upon moisture exposure while the BDDGE surface did not, showing that BADGE adhesives may be more prone to moisture-induced delamination. Lastly, although surface structure can give some insight into adhesion, buried interfacial structures more directly correspond to adhesion properties of polymers. SFG was used to study buried interfaces between deuterated polystyrene (d-PS) and the epoxies before and after moisture exposure. It was shown that moisture exposure acted to disorder the buried interfaces, most likely due to swelling. These results correlated with lap shear adhesion testing showing a decrease in adhesion strength after moisture exposure. The presented work showed that surface and interfacial structures can be correlated to adhesive strength and may be helpful in understanding and designing optimized epoxy underfill adhesives.

Single-Electron Detection and Spectroscopy via Relativistic Cyclotron Radiation.

PubMed

Asner, D M; Bradley, R F; de Viveiros, L; Doe, P J; Fernandes, J L; Fertl, M; Finn, E C; Formaggio, J A; Furse, D; Jones, A M; Kofron, J N; LaRoque, B H; Leber, M; McBride, E L; Miller, M L; Mohanmurthy, P; Monreal, B; Oblath, N S; Robertson, R G H; Rosenberg, L J; Rybka, G; Rysewyk, D; Sternberg, M G; Tedeschi, J R; Thümmler, T; VanDevender, B A; Woods, N L

2015-04-24

It has been understood since 1897 that accelerating charges must emit electromagnetic radiation. Although first derived in 1904, cyclotron radiation from a single electron orbiting in a magnetic field has never been observed directly. We demonstrate single-electron detection in a novel radio-frequency spectrometer. The relativistic shift in the cyclotron frequency permits a precise electron energy measurement. Precise beta electron spectroscopy from gaseous radiation sources is a key technique in modern efforts to measure the neutrino mass via the tritium decay end point, and this work demonstrates a fundamentally new approach to precision beta spectroscopy for future neutrino mass experiments.

Recent advances in multidimensional ultrafast spectroscopy

NASA Astrophysics Data System (ADS)

Oliver, Thomas A. A.

2018-01-01

Multidimensional ultrafast spectroscopies are one of the premier tools to investigate condensed phase dynamics of biological, chemical and functional nanomaterial systems. As they reach maturity, the variety of frequency domains that can be explored has vastly increased, with experimental techniques capable of correlating excitation and emission frequencies from the terahertz through to the ultraviolet. Some of the most recent innovations also include extreme cross-peak spectroscopies that directly correlate the dynamics of electronic and vibrational states. This review article summarizes the key technological advances that have permitted these recent advances, and the insights gained from new multidimensional spectroscopic probes.

Recent advances in multidimensional ultrafast spectroscopy

PubMed Central

2018-01-01

Multidimensional ultrafast spectroscopies are one of the premier tools to investigate condensed phase dynamics of biological, chemical and functional nanomaterial systems. As they reach maturity, the variety of frequency domains that can be explored has vastly increased, with experimental techniques capable of correlating excitation and emission frequencies from the terahertz through to the ultraviolet. Some of the most recent innovations also include extreme cross-peak spectroscopies that directly correlate the dynamics of electronic and vibrational states. This review article summarizes the key technological advances that have permitted these recent advances, and the insights gained from new multidimensional spectroscopic probes. PMID:29410844

Precision Saturated Absorption Spectroscopy of H3+

NASA Astrophysics Data System (ADS)

Guan, Yu-chan; Liao, Yi-Chieh; Chang, Yung-Hsiang; Peng, Jin-Long; Shy, Jow-Tsong

2016-06-01

In our previous work on the Lamb dips of the νb{2} fundamental band of H3+, the saturated absorption spectrum was obtained by the third-derivative spectroscopy using frequency modulation [1]. However, the frequency modulation also causes error in absolute frequency determination. To solve this problem, we have built an offset-locking system to lock the OPO pump frequency to an iodine-stabilized Nd:YAG laser. With this modification, we are able to scan the OPO idler frequency precisely and obtain the profile of the Lamb dips. Double modulation (amplitude modulation of the idler power and concentration modulation of the ion) is employed to subtract the interference fringes of the signal and increase the signal-to-noise ratio effectively. To Determine the absolute frequency of the idler wave, the pump wave is offset locked on the R(56) 32-0 a10 hyperfine component of 127I2, and the signal wave is locked on a GPS disciplined fiber optical frequency comb (OFC). All references and lock systems have absolute frequency accuracy better than 10 kHz. Here, we demonstrate its performance by measuring one transition of methane and sixteen transitions of H3+. This instrument could pave the way for the high-resolution spectroscopy of a variety of molecular ions. [1] H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, and J.-T. Shy, Phys. Rev. Lett. 109, 263002 (2012).

Dielectric spectroscopy in agrophysics

NASA Astrophysics Data System (ADS)

Skierucha, W.; Wilczek, A.; Szypłowska, A.

2012-04-01

The paper presents scientific foundation and some examples of agrophysical applications of dielectric spectroscopy techniques. The aim of agrophysics is to apply physical methods and techniques for studies of materials and processes which occur in agriculture. Dielectric spectroscopy, which describes the dielectric properties of a sample as a function of frequency, may be successfully used for examinations of properties of various materials. Possible test materials may include agrophysical objects such as soil, fruit, vegetables, intermediate and final products of the food industry, grain, oils, etc. Dielectric spectroscopy techniques enable non-destructive and non-invasive measurements of the agricultural materials, therefore providing tools for rapid evaluation of their water content and quality. There is a limited number of research in the field of dielectric spectroscopy of agricultural objects, which is caused by the relatively high cost of the respective measurement equipment. With the fast development of modern technology, especially in high frequency applications, dielectric spectroscopy has great potential of expansion in agrophysics, both in cognitive and utilitarian aspects.

Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlatemore » with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. It was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.« less

Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlatemore » with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.« less

Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

DOE PAGES

Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; ...

2015-10-14

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlatemore » with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.« less

Millimeter and Sub-millimeter High Resolution Spectroscopy: New Frontiers with ALMA

NASA Astrophysics Data System (ADS)

Ziurys, Lucy M.

2016-06-01

It is becoming increasingly clear that new laboratory data will be critical for the next decade of observations with the Atacama Large Millimeter Array (ALMA). The high spatial resolution offered by ALMA will probe new regions of molecular complexity, including the inner envelopes of evolved stars, regions dominated by UV radiation, and the densest cores of molecular clouds. New molecular lines will be discovered in the wide wavelength range covered by the ALMA bands, and high resolution, gas-phase spectroscopy are needed to provide crucial “rest frequencies.” In particular, highly accurate methods that measure millimeter and sub-millimeter rotational transitions, such as direct absorption and Fourier transform mm-wave techniques, are important, especially when coupled to exotic molecular production schemes. Recent ALMA studies of SH+ and larger organic species have already demonstrated the need for laboratory measurements. New laboratory work will likely be required for circumstellar refractory molecules, radicals and ions generated near photon-dominated regions (PDRs), and large, organic-type species. This talk will give an overview of current contributions of laboratory spectroscopy to ALMA observations, summarize relevant spectroscopic techniques, and provide input into future prospects and directions.

On-chip dual-comb source for spectroscopy

PubMed Central

Dutt, Avik; Joshi, Chaitanya; Ji, Xingchen; Cardenas, Jaime; Okawachi, Yoshitomo; Luke, Kevin; Gaeta, Alexander L.; Lipson, Michal

2018-01-01

Dual-comb spectroscopy is a powerful technique for real-time, broadband optical sampling of molecular spectra, which requires no moving components. Recent developments with microresonator-based platforms have enabled frequency combs at the chip scale. However, the need to precisely match the resonance wavelengths of distinct high quality-factor microcavities has hindered the development of on-chip dual combs. We report the simultaneous generation of two microresonator combs on the same chip from a single laser, drastically reducing experimental complexity. We demonstrate broadband optical spectra spanning 51 THz and low-noise operation of both combs by deterministically tuning into soliton mode-locked states using integrated microheaters, resulting in narrow (<10 kHz) microwave beat notes. We further use one comb as a reference to probe the formation dynamics of the other comb, thus introducing a technique to investigate comb evolution without auxiliary lasers or microwave oscillators. We demonstrate high signal-to-noise ratio absorption spectroscopy spanning 170 nm using the dual-comb source over a 20-μs acquisition time. Our device paves the way for compact and robust spectrometers at nanosecond time scales enabled by large beat-note spacings (>1 GHz). PMID:29511733

Ultrasonic Resonance Spectroscopy of Composite Rings for Flywheel Rotors

NASA Technical Reports Server (NTRS)

Harmon, Laura M.; Baaklini, George Y.

2001-01-01

Flywheel energy storage devices comprising multilayered composite rotor systems are being studied extensively for utilization in the International Space Station. These composite material systems were investigated with a recently developed ultrasonic resonance spectroscopy technique. The system employs a swept frequency approach and performs a fast Fourier transform on the frequency spectrum of the response signal. In addition. the system allows for equalization of the frequency spectrum, providing all frequencies with equal amounts of energy to excite higher order resonant harmonics. Interpretation of the second fast Fourier transform, along with equalization of the frequency spectrum, offers greater assurance in acquiring and analyzing the fundamental frequency, or spectrum resonance spacing. The range of frequencies swept in a pitch-catch mode was varied up to 8 MHz, depending on the material and geometry of the component. Single and multilayered material samples, with and without known defects, were evaluated to determine how the constituents of a composite material system affect the resonant frequency. Amplitude and frequency changes in the spectrum and spectrum resonance spacing domains were examined from ultrasonic responses of a flat composite coupon, thin composite rings, and thick composite rings. Also, the ultrasonic spectroscopy responses from areas with an intentional delamination and a foreign material insert, similar to defects that may occur during manufacturing malfunctions, were compared with those from defect-free areas in thin composite rings. A thick composite ring with varying thickness was tested to investigate the full-thickness resonant frequency and any possible bulk interfacial bond issues. Finally, the effect on the frequency response of naturally occurring single and clustered voids in a composite ring was established.

Study of Pulsations in the Atmosphere of the roAp star HD 137949

NASA Astrophysics Data System (ADS)

Sachkov, M.; Hareter, M.; Ryabchikova, T.; Wade, G.; Kochukhov, O.; Weiss, W. W.

The roAp star HD 137949 (33 Lib) shows the most complex pulsational behaviour among all roAp stars. Mkrtichian et al. (2003) found nearly anti-phase pulsations of Nd II and Nd III lines, which they attribute to the presence of a pulsation node high in the atmosphere of HD 137949. This was confirmed by Kurtz at al. (2005), who also find that in some REE lines the main frequency, corresponding to 8.27 min, and its harmonic have almost equal RV amplitudes. Based on high accuracy observations Ryabchikova et al. (2007a) studied pulsational characteristics of the HD 137949 atmosphere in detail. In general, spectroscopy provides 3D resolution of modes and allows to search for the photometrically undetectable frequencies. The high-accuracy space photometry provides very high-precision measurements of detected pulsation frequencies and enables an accurate phasing of multi-site spectroscopic data. A combination of simultaneous spectroscopy and photometry represents the most sophisticated asteroseismic dataset for any roAp star. In 2009 the star HD 137949 became a target of an intense observing campaign that combined ground-based spectroscopy with space photometry, obtained with the MOST satellite. We collected 780 spectra using the ESPaDOnS spectrograph mounted on the 3.6 m CFHT telescope; 374 spectra were obtained with the FIES spectrograph mounted on the 2.56-m NOT to perform the time-resolved spectroscopy of HD 137949. In addition, we used 111 UVES spectra (2004) from the ESO archive to check the mode stability. The frequency analysis of the new radial velocity (RV) measurements confirmed the previously reported frequency pattern (two frequencies and the first harmonic of the main frequency), and revealed an additional frequency at 1.991 mHz. The new frequency solution fits perfectly the RV variations from the 2004 and 2009 observational sets providing a strong support for the p-mode stability in the roAp star HD 137949 for at least 5 years.

Bibliography of Soviet Laser Developments, September-October 1987

DTIC Science & Technology

1988-10-01

Lasers , Gas Lasers , Chemical Lasers , Laser Components Nonlinear Optics, Spectroscopy of Laser Materials, Ultrashort Pulse Generation, Laser ...optics; spectroscopy of laser materials; ultrashort pulse generation; crystal growing; theoretical aspects of advanced lasers ; and general laser theory...focusing ....................... 26 6. Acoustic Interaction ................ 26 G. Spectroscopy of Laser Materials ......... 28 H.

Offset-frequency locking of extended-cavity diode lasers for precision spectroscopy of water at 1.38 μm.

PubMed

Gianfrani, Livio; Castrillo, Antonio; Fasci, Eugenio; Galzerano, Gianluca; Casa, Giovanni; Laporta, Paolo

2010-10-11

We describe a continuous-wave diode laser spectrometer for water-vapour precision spectroscopy at 1.38 μm. The spectrometer is based upon the use of a simple scheme for offset-frequency locking of a pair of extended-cavity diode lasers that allows to achieve unprecedented accuracy and reproducibility levels in measuring molecular absorption. When locked to the master laser with an offset frequency of 1.5 GHz, the slave laser exhibits residual frequency fluctuations of 1 kHz over a time interval of 25 minutes, for a 1-s integration time. The slave laser could be continuously tuned up to 3 GHz, the scan showing relative deviations from linearity below the 10{-6} level. Simultaneously, a capture range of the order of 1 GHz was obtained. Quantitative spectroscopy was also demonstrated by accurately determining relevant spectroscopic parameters for the 22,1→22,0line of the H2(18)O v1+v3 band at 1384.6008 nm.

Towards Breath Gas Analysis Based on Millimeter-Wave Molecular Spectroscopy

NASA Astrophysics Data System (ADS)

Rothbart, Nick; Hübers, Heinz-Wilhelm; Schmalz, Klaus; Borngräber, Johannes; Kissinger, Dietmar

2018-03-01

Breath gas analysis is a promising non-invasive tool for medical diagnosis as there are thousands of Volatile Organic Compounds (VOCs) in human breath that can be used as health monitoring markers. Millimeter-wave/terahertz molecular spectroscopy is highly suitable for breath gas analysis due to unique fingerprint spectra of many VOCs in that frequency range. We present our recent work on sensor systems for gas spectroscopy based on integrated transmitters (TX) and receivers (RX) fabricated in IHP's 0.13 μm SiGe BiCMOS technology. For a single-band system, spectroscopic measurements and beam profiles are presented. The frequency is tuned by direct voltage-frequency tuning and by a fractional-n PLL, respectively. The spectroscopic system includes a folded gas absorption cell with gas pre-concentration abilities demonstrating the detection of a 50 ppm mixture of ethanol in ambient air corresponding to a minimum detectable concentration of 260 ppb. Finally, the design of a 3-band system covering frequencies from 225 to 273 GHz is introduced.

A theoretical description of the polarization dependence of the sum frequency generation spectroscopy of the water/vapor interface

NASA Astrophysics Data System (ADS)

Perry, Angela; Neipert, Christine; Kasprzyk, Christina Ridley; Green, Tony; Space, Brian; Moore, Preston B.

2005-10-01

An improved time correlation function (TCF) description of sum frequency generation (SFG) spectroscopy was developed and applied to theoretically describing the spectroscopy of the ambient water/vapor interface. A more general TCF expression than was published previously is presented—it is valid over the entire vibrational spectrum for both the real and imaginary parts of the signal. Computationally, earlier time correlation function approaches were limited to short correlation times that made signal processing challenging. Here, this limitation is overcome, and well-averaged spectra are presented for the three independent polarization conditions that are possible for electronically nonresonant SFG. The theoretical spectra compare quite favorably in shape and relative magnitude to extant experimental results in the O H stretching region of water for all polarization geometries. The methodological improvements also allow the calculation of intermolecular SFG spectra. While the intermolecular spectrum of bulk water shows relatively little structure, the interfacial spectra (for polarizations that are sensitive to dipole derivatives normal to the interface—SSP and PPP) show a well-defined intermolecular mode at 875cm-1 that is comparable in intensity to the rest of the intermolecular structure, and has an intensity that is approximately one-sixth of the magnitude of the intense free OH stretching peak. Using instantaneous normal mode methods, the resonance is shown to be due to a wagging mode localized on a single water molecule, almost parallel to the interface, with two hydrogens displaced normal to the interface, and the oxygen anchored in the interface. We have also uncovered the origin of another intermolecular mode at 95cm-1 for the SSP and PPP spectra, and at 220cm-1 for the SPS spectra. These resonances are due to hindered translations perpendicular to the interface for the SSP and PPP spectra, and translations parallel to the interface for the SPS spectra. Further, by examining the real and imaginary parts of the SFG signal, several resonances are shown to be due to a single spectroscopic species while the "donor" OH region is shown to consist of three distinct species—consistent with an earlier experimental analysis.

High density terahertz frequency comb produced by coherent synchrotron radiation

PubMed Central

Tammaro, S.; Pirali, O.; Roy, P.; Lampin, J.-F.; Ducournau, G.; Cuisset, A.; Hindle, F.; Mouret, G.

2015-01-01

Frequency combs have enabled significant progress in frequency metrology and high-resolution spectroscopy extending the achievable resolution while increasing the signal-to-noise ratio. In its coherent mode, synchrotron radiation is accepted to provide an intense terahertz continuum covering a wide spectral range from about 0.1 to 1 THz. Using a dedicated heterodyne receiver, we reveal the purely discrete nature of this emission. A phase relationship between the light pulses leads to a powerful frequency comb spanning over one decade in frequency. The comb has a mode spacing of 846 kHz, a linewidth of about 200 Hz, a fractional precision of about 2 × 10−10 and no frequency offset. The unprecedented potential of the comb for high-resolution spectroscopy is demonstrated by the accurate determination of pure rotation transitions of acetonitrile. PMID:26190043

Active mode locking of quantum cascade lasers in an external ring cavity.

PubMed

Revin, D G; Hemingway, M; Wang, Y; Cockburn, J W; Belyanin, A

2016-05-05

Stable ultrashort light pulses and frequency combs generated by mode-locked lasers have many important applications including high-resolution spectroscopy, fast chemical detection and identification, studies of ultrafast processes, and laser metrology. While compact mode-locked lasers emitting in the visible and near infrared range have revolutionized photonic technologies, the systems operating in the mid-infrared range where most gases have their strong absorption lines, are bulky and expensive and rely on nonlinear frequency down-conversion. Quantum cascade lasers are the most powerful and versatile compact light sources in the mid-infrared range, yet achieving their mode-locked operation remains a challenge, despite dedicated effort. Here we report the demonstration of active mode locking of an external-cavity quantum cascade laser. The laser operates in the mode-locked regime at room temperature and over the full dynamic range of injection currents.

Active mode locking of quantum cascade lasers in an external ring cavity

PubMed Central

Revin, D. G.; Hemingway, M.; Wang, Y.; Cockburn, J. W.; Belyanin, A.

2016-01-01

Stable ultrashort light pulses and frequency combs generated by mode-locked lasers have many important applications including high-resolution spectroscopy, fast chemical detection and identification, studies of ultrafast processes, and laser metrology. While compact mode-locked lasers emitting in the visible and near infrared range have revolutionized photonic technologies, the systems operating in the mid-infrared range where most gases have their strong absorption lines, are bulky and expensive and rely on nonlinear frequency down-conversion. Quantum cascade lasers are the most powerful and versatile compact light sources in the mid-infrared range, yet achieving their mode-locked operation remains a challenge, despite dedicated effort. Here we report the demonstration of active mode locking of an external-cavity quantum cascade laser. The laser operates in the mode-locked regime at room temperature and over the full dynamic range of injection currents. PMID:27147409

thin film capacitors

NASA Astrophysics Data System (ADS)

Bodeux, Romain; Gervais, Monique; Wolfman, Jérôme; Gervais, François

2014-09-01

CaCu3Ti4O12 (CCTO) thin films were grown by pulsed laser deposition on Pt and La0.9Sr1.1NiO4 (LSNO) bottom electrodes. The electrical characteristics of the CCTO/Pt and CCTO/LSNO Schottky junctions have been analyzed by impedance spectroscopy, capacitance-voltage (C-V) and current-voltage (I-V) measurements as a function of frequency (40 Hz-1 MHz) and temperature (300-475 K). Similar results were obtained for the two Schottky diodes. The conduction mechanism through the Schottky junctions was described using a thermionic emission model and the electrical parameters were determined. The strong deviation from the ideal I-V characteristics and the increase in capacitance at low frequency for -0.5 V bias are in agreement with the presence of traps near the interfaces. Results point toward the important effect of defects generated at the interface by deposition of CCTO.

Advanced Non-Destructive Assessment Technology to Determine the Aging of Silicon Containing Materials for Generation IV Nuclear Reactors

NASA Astrophysics Data System (ADS)

Koenig, T. W.; Olson, D. L.; Mishra, B.; King, J. C.; Fletcher, J.; Gerstenberger, L.; Lawrence, S.; Martin, A.; Mejia, C.; Meyer, M. K.; Kennedy, R.; Hu, L.; Kohse, G.; Terry, J.

2011-06-01

To create an in-situ, real-time method of monitoring neutron damage within a nuclear reactor core, irradiated silicon carbide samples are examined to correlate measurable variations in the material properties with neutron fluence levels experienced by the silicon carbide (SiC) during the irradiation process. The reaction by which phosphorus doping via thermal neutrons occurs in the silicon carbide samples is known to increase electron carrier density. A number of techniques are used to probe the properties of the SiC, including ultrasonic and Hall coefficient measurements, as well as high frequency impedance analysis. Gamma spectroscopy is also used to examine residual radioactivity resulting from irradiation activation of elements in the samples. Hall coefficient measurements produce the expected trend of increasing carrier concentration with higher fluence levels, while high frequency impedance analysis shows an increase in sample impedance with increasing fluence.

Alcohol Oxidation at Platinum–Gas and Platinum–Liquid Interfaces: The Effect of Platinum Nanoparticle Size, Water Coadsorption, and Alcohol Concentration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tatsumi, Hironori; Liu, Fudong; Han, Hui-Ling

Platinum nanoparticles size range from 1 to 8 nm deposited on mesoporous silica MCF-17 catalyzed alcohol oxidations were studied in the gas and liquid phases. Among methanol, ethanol, 2- propanol and 2-butanol reactions, the turnover frequency increased with Pt nanoparticle size for all the alcohols utilized. The activation energies for the oxidations were almost same among all alcohol species, but higher in the gas phase than those in the liquid phase. Water coadsorption poisoned the reaction in the gas phase, while it increased the reaction turnover rates in the liquid phase. Sum frequency generation (SFG) vibrational spectroscopy studies and DFTmore » calculations revealed that the alcohol molecules pack horizontally on the metal surface in low concentrations and stand up in high concentrations, which affect the dissociation of β-hydrogen of the alcohols as the critical step in alcohol oxidations.« less

Alcohol Oxidation at Platinum–Gas and Platinum–Liquid Interfaces: The Effect of Platinum Nanoparticle Size, Water Coadsorption, and Alcohol Concentration

DOE PAGES

Tatsumi, Hironori; Liu, Fudong; Han, Hui-Ling; ...

2017-03-21

Platinum nanoparticles size range from 1 to 8 nm deposited on mesoporous silica MCF-17 catalyzed alcohol oxidations were studied in the gas and liquid phases. Among methanol, ethanol, 2- propanol and 2-butanol reactions, the turnover frequency increased with Pt nanoparticle size for all the alcohols utilized. The activation energies for the oxidations were almost same among all alcohol species, but higher in the gas phase than those in the liquid phase. Water coadsorption poisoned the reaction in the gas phase, while it increased the reaction turnover rates in the liquid phase. Sum frequency generation (SFG) vibrational spectroscopy studies and DFTmore » calculations revealed that the alcohol molecules pack horizontally on the metal surface in low concentrations and stand up in high concentrations, which affect the dissociation of β-hydrogen of the alcohols as the critical step in alcohol oxidations.« less

Terahertz Spectroscopy for Chemical Detection and Burn Characterization

NASA Astrophysics Data System (ADS)

Arbab, Mohammad Hassan

Terahertz (THz) frequencies represent the last frontier of the electromagnetic spectrum to be investigated by scientists. One of the main attractions of investigating this frequency range is the richness of the spectral information that can be obtained using a Terahertz Time-Domain Spectroscopy (THz-TDS) setup. Many large molecule chemicals and polymers have vibrational and rotational modes in the THz frequencies. Study of these resonance modes has revealed a wealth of new information about the intermolecular structure, and its transformation during crystallization or polymerization process. This information helps researchers develop new materials to address problems such as efficient energy conversion in polymer solar cells. Moreover, similar signature-like terahertz modes can be used for stand-off identification of substances or for nondestructive evaluation of defects in industrial applications. Finally, terahertz spectroscopy has the potential to provide a safe and non-ionizing imaging modality to study cellular and molecular events in biological and biomedical applications. The high sensitivity of terahertz waves to attenuation by both bound and free water molecules can also provides a source of signal contrast for many future biomedical imaging and diagnostic applications. In this dissertation, we aim to study and develop three such applications of terahertz spectroscopy, which form the three axes of our work: rough-surface scattering mediated stand-off detection of chemicals, characterization of burn injuries using terahertz radiation, and a new electrically tunable bandpass filter device incorporating nano-material transparent electrodes that can enable fast terahertz spectroscopy in the frequency domain.

Two-Photon Absorption Spectroscopy of Rubidium with a Dual-Comb Tequnique

NASA Astrophysics Data System (ADS)

Nishiyama, Akiko; Yoshida, Satoru; Hariki, Takuya; Nakajima, Yoshiaki; Minoshima, Kaoru

2017-06-01

Dual-comb spectroscopies have great potential for high-resolution molecular and atomic spectroscopies, thanks to the broadband comb spectrum consisting of dense narrow modes. In this study, we apply the dual-comb system to Doppler-free two-photon absorption spectroscopy. The outputs of two frequency combs excite several two-photon transitions of rubidium, and we obtained broadband Doppler-free spectra from dual-comb fluorescence signals. The fluorescence detection scheme circumvents the sensitivity limit which is effectively determined by the dynamic range of photodetectors in absorption-based dual-comb spectroscopies. Our system realized high-sensitive, Doppler-free high-resolution and broadband atomic spectroscopy. A part of observed spectra of 5S_{1/2} - 5D_{5/2} transition is shown in the figure. The hyperfine structures of the F" = 1 - F' = 3,2,1 transitions are fully-resolved and the spectral widths are approximately 5 MHz. The absolute frequency axis is precisely calibrated from comb mode frequencies which were stabilized to a GPS-disciplined clock. This work was supported by JST through the ERATO MINOSHIMA Intelligent Optical Synthesizer Project and Grant-in-Aid for JSPS Fellows (16J02345). A. Nishiyama, S. Yoshida, Y. Nakajima, H. Sasada, K. Nakagawa, A. Onae, K. and Minoshima, Opt. Express 24, 25894 (2016). A. Hipke, S. A. Meek, T. Ideguchi, T.W. Hänsch, and N. Picqué, Phys. Rev. A 90, 011805(R) (2014).

High-accuracy deep-UV Ramsey-comb spectroscopy in krypton

NASA Astrophysics Data System (ADS)

Galtier, Sandrine; Altmann, Robert K.; Dreissen, Laura S.; Eikema, Kjeld S. E.

2017-01-01

In this paper, we present a detailed account of the first precision Ramsey-comb spectroscopy in the deep UV. We excite krypton in an atomic beam using pairs of frequency-comb laser pulses that have been amplified to the millijoule level and upconverted through frequency doubling in BBO crystals. The resulting phase-coherent deep-UV pulses at 212.55 nm are used in the Ramsey-comb method to excite the two-photon 4p^6 → 4p^5 5p [1/2 ]_0 transition. For the {}^{84}Kr isotope, we find a transition frequency of 2829833101679(103) kHz. The fractional accuracy of 3.7 × 10^{-11} is 34 times better than previous measurements, and also the isotope shifts are measured with improved accuracy. This demonstration shows the potential of Ramsey-comb excitation for precision spectroscopy at short wavelengths.

Generation of continuous-wave 194 nm laser for mercury ion optical frequency standard

NASA Astrophysics Data System (ADS)

Zou, Hongxin; Wu, Yue; Chen, Guozhu; Shen, Yong; Liu, Qu; Precision measurement; atomic clock Team

2015-05-01

194 nm continuous-wave (CW) laser is an essential part in mercury ion optical frequency standard. The continuous-wave tunable radiation sources in the deep ultraviolet (DUV) region of the spectrum is also serviceable in high-resolution spectroscopy with many atomic and molecular lines. We introduce a scheme to generate continuous-wave 194 nm radiation with SFM in a Beta Barium Borate (BBO) crystal here. The two source beams are at 718 nm and 266 nm, respectively. Due to the property of BBO, critical phase matching (CPM) is implemented. One bow-tie cavity is used to resonantly enhance the 718 nm beam while the 266 nm makes a single pass, which makes the configuration easy to implement. Considering the walk-off effect in CPM, the cavity mode is designed to be elliptical so that the conversion efficiency can be promoted. Since the 266 nm radiation is generated by a 532 nm laser through SHG in a BBO crystal with a large walk-off angle, the output mode is quite non-Gaussian. To improve mode matching, we shaped the 266 nm beam into Gaussian modes with a cylindrical lens and iris diaphragm. As a result, 2.05 mW 194 nm radiation can be generated. As we know, this is the highest power for 194 nm CW laser using SFM in BBO with just single resonance. The work is supported by the National Natural Science Foundation of China (Grant No. 91436103 and No. 11204374).

Graphene/cobalt nanocarrier for hyperthermia therapy and MRI diagnosis.

PubMed

Hatamie, Shadie; Ahadian, Mohammad Mahdi; Ghiass, Mohammad Adel; Iraji Zad, Azam; Saber, Reza; Parseh, Benyamin; Oghabian, Mohammad Ali; Shanehsazzadeh, Saeed

2016-10-01

Graphene/cobalt nanocomposites are promising materials for theranostic nanomedicine applications, which are defined as the ability to diagnose, provide targeted therapy and monitor the response to the therapy. In this study, the composites were synthesized via chemical method, using graphene oxide as the source material and assembling cobalt nanoparticles of 15nm over the surface of graphene sheets. Various characterization techniques were then employed to reveal the morphology, size and structure of the nanocomposites, such as X-ray diffraction analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, high resolution transmission electron microscopy and ultraviolet visible spectroscopy. Using ion-coupled plasma optical emission spectroscopy, cobalt concentration in the nanocomposites was found to be 80%. In addition, cytotoxicity of graphene/cobalt nanocomposites were evaluated using 3-[4,5-dimethylthiazol-2yl]-2,5-diphenyltetrazolium bromide or MTT assay. MTT viability assay exhibited biocompatibility to L929 mouse fibroblasts cells, under a high dose of 100μg/mL over 24h. Hyperthermia results showed the superior conversion of electromagnetic energy into heat at 350kHz frequency for 0.01 and 0.005g/L of the nanocomposites solution. The measured heat generation and energy transfer results were anticipated by the finite element analysis, conducted for the 3D structure. Magnetic resonance imaging characteristics also showed that negatively charge graphene/cobalt nanocomposites are suitable for T1-weighted imaging. Copyright © 2016 Elsevier B.V. All rights reserved.

Multi-frequency data analysis in AFM by wavelet transform

NASA Astrophysics Data System (ADS)

Pukhova, V.; Ferrini, G.

2017-10-01

Interacting cantilevers in AFM experiments generate non-stationary, multi-frequency signals consisting of numerous excited flexural and torsional modes and their harmonics. The analysis of such signals is challenging, requiring special methodological approaches and a powerful mathematical apparatus. The most common approach to the signal analysis is to apply Fourier transform analysis. However, FT gives accurate spectra for stationary signals, and for signals changing their spectral content over time, FT provides only an averaged spectrum. Hence, for non-stationary and rapidly varying signals, such as those from interacting cantilevers, a method that shows the spectral evolution in time is needed. One of the most powerful techniques, allowing detailed time-frequency representation of signals, is the wavelet transform. It is a method of analysis that allows representation of energy associated to the signal at a particular frequency and time, providing correlation between the spectral and temporal features of the signal, unlike FT. This is particularly important in AFM experiments because signals nonlinearities contains valuable information about tip-sample interactions and consequently surfaces properties. The present work is aimed to show the advantages of wavelet transform in comparison with FT using as an example the force curve analysis in dynamic force spectroscopy.

Complex magnetic susceptibility setup for spectroscopy in the extremely low-frequency range.

PubMed

Kuipers, B W M; Bakelaar, I A; Klokkenburg, M; Erné, B H

2008-01-01

A sensitive balanced differential transformer was built to measure complex initial parallel magnetic susceptibility spectra in the 0.01-1000 Hz range. The alternating magnetic field can be chosen sufficiently weak that the magnetic structure of the samples is only slightly perturbed and the low frequencies make it possible to study the rotational dynamics of large magnetic colloidal particles or aggregates dispersed in a liquid. The distinguishing features of the setup are the novel multilayered cylindrical coils with a large sample volume and a large number of secondary turns (55 000) to measure induced voltages with a good signal-to-noise ratio, the use of a dual channel function generator to provide an ac current to the primary coils and an amplitude- and phase-adjusted compensation voltage to the dual phase differential lock-in amplifier, and the measurement of several vector quantities at each frequency. We present the electrical impedance characteristics of the coils, and we demonstrate the performance of the setup by measurement on magnetic colloidal dispersions covering a wide range of characteristic relaxation frequencies and magnetic susceptibilities, from chi approximately -10(-5) for pure water to chi>1 for concentrated ferrofluids.

High power and spectral purity continuous-wave photonic THz source tunable from 1 to 4.5 THz for nonlinear molecular spectroscopy

NASA Astrophysics Data System (ADS)

Kiessling, J.; Breunig, I.; Schunemann, P. G.; Buse, K.; Vodopyanov, K. L.

2013-10-01

We report a diffraction-limited photonic terahertz (THz) source with linewidth <10 MHz that can be used for nonlinear THz studies in the continuous wave (CW) regime with uninterrupted tunability in a broad range of THz frequencies. THz output is produced in orientation-patterned (OP) gallium arsenide (GaAs) via intracavity frequency mixing between the two closely spaced resonating signal and idler waves of an optical parametric oscillator (OPO) operating near λ = 2 μm. The doubly resonant type II OPO is based on a periodically poled lithium niobate (PPLN) pumped by a single-frequency Yb:YAG disc laser at 1030 nm. We take advantage of the enhancement of both optical fields inside a high-finesse OPO cavity: with 10 W of 1030 nm pump, 100 W of intracavity power near 2 μm was attained with GaAs inside cavity. This allows dramatic improvement in terms of generated THz power, as compared to the state-of-the art CW methods. We achieved >25 μW of single-frequency tunable CW THz output power scalable to >1 mW with proper choice of pump laser wavelength.

Determination of a potential quantitative measure of the state of the lung using lung ultrasound spectroscopy.

PubMed

Demi, Libertario; van Hoeve, Wim; van Sloun, Ruud J G; Soldati, Gino; Demi, Marcello

2017-10-06

B-lines are ultrasound-imaging artifacts, which correlate with several lung-pathologies. However, their understanding and characterization is still largely incomplete. To further study B-lines, lung-phantoms were developed by trapping a layer of microbubbles in tissue-mimicking gel. To simulate the alveolar size reduction typical of various pathologies, 170 and 80 µm bubbles were used for phantom-type 1 and 2, respectively. A normal alveolar diameter is approximately 280 µm. A LA332 linear-array connected to the ULA-OP platform was used for imaging. Standard ultrasound (US) imaging at 4.5 MHz was performed. Subsequently, a multi-frequency approach was used where images were sequentially generated using orthogonal sub-bands centered at different frequencies (3, 4, 5, and 6 MHz). Results show that B-lines appear predominantly with phantom-type 2. Moreover, the multi-frequency approach revealed that the B-lines originate from a specific portion of the US spectrum. These results can give rise to significant clinical applications since, if further confirmed by extensive in-vivo studies, the native frequency of B-lines could provide a quantitative-measure of the state of the lung.

Laser-based sensor for detection of hazardous gases in the air using waveguide CO2 laser.

PubMed

Gondal, Mohammed A; Bakhtiari, Imran A; Dastageer, Abdul K

2007-06-01

A spectrometer based on the principle of photoacoustic spectroscopy has been developed recently at our laboratory for the detection of hazardous gases such as O3, C2H4, SO2, NO2 and SF6. In most of our earlier works, we employed a mechanical chopper to modulate the laser beam and this chopper modulation has the crucial disadvantage of instability in the chopper frequency. Even a minor shift of about 1 Hz in the modulation frequency could significantly reduce the photoacoustic signal by an order of magnitude at the acoustic resonant mode of the photoacoustic cell. To overcome this problem, we developed a photoacoustic spectrometer where a wave guided CW CO2 laser beam is modulated electronically with the external frequency generator. Our preliminary results show that the electronic modulation of CO2 laser beam improved the sensitivity of our spectrometer by a factor of 6. The parametric dependence of photoacoustic signal on laser power, modulation frequency and trace gas concentration, was investigated and the comparison between the two modulation techniques is presented in this paper for detection of trace gases such as C2H4.

Current-induced modulation of backward spin-waves in metallic microstructures

NASA Astrophysics Data System (ADS)

Sato, Nana; Lee, Seo-Won; Lee, Kyung-Jin; Sekiguchi, Koji

2017-03-01

We performed a propagating spin-wave spectroscopy for backward spin-waves in ferromagnetic metallic microstructures in the presence of electric-current. Even with the smaller current injection of 5× {{10}10} A m-2 into ferromagnetic microwires, the backward spin-waves exhibit a gigantic 200 MHz frequency shift and a 15% amplitude change, showing 60 times larger modulation compared to previous reports. Systematic experiments by measuring dependences on a film thickness of mirowire, on the wave-vector of spin-wave, and on the magnitude of bias field, we revealed that for the backward spin-waves a distribution of internal magnetic field generated by electric-current efficiently modulates the frequency and amplitude of spin-waves. The gigantic frequency and amplitude changes were reproduced by a micromagnetics simulation, predicting that the current-injection of 5× {{10}11} A m-2 allows 3 GHz frequency shift. The effective coupling between electric-current and backward spin-waves has a potential to build up a logic control method which encodes signals into the phase and amplitude of spin-waves. The metallic magnonics cooperating with electronics could suggest highly integrated magnonic circuits both in Boolean and non-Boolean principles.

Novel Concept of Frequency-Combs Interferometric Spectroscopy in the Mid-IR for Significantly Enhanced Detection of Explosives

DTIC Science & Technology

2015-12-01

frequency combs. Ultrasensitive detection of methane, isotopic carbon dioxide, carbon monoxide, formaldehyde, acetylene, and ethylene was performed in...rmaldehyde, acetylene, and ethylene was perfo rmed in the spectral range 2.5- 5 11111 using intracav ity spectroscopy in broadband optical parametric osc...trace point detection of methane, carbon dioxide, isotopic (13C02) carbon dioxide, carbon monoxide, ethylene , acetylene, and formaldehyde and

Nonlinear acoustic spectroscopy of cracked flaws and disbonds: Fundamentals, techniques, and applications

NASA Astrophysics Data System (ADS)

Maev, R. Gr.; Solodov, I. Yu.

2000-05-01

Classical nonlinear acoustics of solids operates with distributed material nonlinearity related to unharmonicity of molecular interaction forces. Weakening of molecular bonds in a defect area or intermittent lack of elastic coupling between the faces of a vibrating crack or unbond ("clapping") results in anomalously high local contact acoustic nonlinearity (CAN). CAN properties and spectral features are different from those of the classical analog and important to develop new acoustic NDE techniques. Three approaches to nonlinear NDE methodology have been experimentally verified: low-frequency (hundreds of Hz) vibration technique, intermediate-frequency (hundreds of kHz) standing wave and high-frequency (tens of MHz) propagation modes. Low-frequency nonlinear contact vibrations revealed multiple sub- and super-harmonics generation featuring non-monotonous (sinx/x type) spectra. Parametric instability observed in resonator with a nonlinear contact leads to the output spectrum splitting up into successive sub-harmonics as the wave amplitude increases. High-frequency experiments demonstrated abnormal increases in the third harmonic amplitude: 3 or 4 order enhancement of the 3-ω nonlinear parameter was measured for the nonlinear contact. The CAN spectral features in both acoustic and vibration modes were used for nonlinear NDE of simulated and realistic flaws in glass, metal welds, etc. The sensitivities of the techniques are compared and their practical applicability assessed.

Static and Dynamic Measurement of Dopamine Adsorption in Carbon Fiber Microelectrodes Using Electrochemical Impedance Spectroscopy.

PubMed

Rivera-Serrano, Nilka; Pagan, Miraida; Colón-Rodríguez, Joanisse; Fuster, Christian; Vélez, Román; Almodovar-Faria, Jose; Jiménez-Rivera, Carlos; Cunci, Lisandro

2018-02-06

In this study, electrochemical impedance spectroscopy was used for the first time to study the adsorption of dopamine in carbon fiber microelectrodes. In order to show a proof-of-concept, static and dynamic measurements were taken at potentials ranging from -0.4 to 0.8 V versus Ag|AgCl to demonstrate the versatility of this technique to study dopamine without the need of its oxidation. We used electrochemical impedance spectroscopy and single frequency electrochemical impedance to measure different concentrations of dopamine as low as 1 nM. Moreover, the capacitance of the microelectrodes surface was found to decrease due to dopamine adsorption, which is dependent on its concentration. The effect of dissolved oxygen and electrochemical oxidation of the surface in the detection of dopamine was also studied. Nonoxidized and oxidized carbon fiber microelectrodes were prepared and characterized by optical microscopy, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Optimum working parameters of the electrodes, such as frequency and voltage, were obtained for better measurement. Electrochemical impedance of dopamine was determined at different concentration, voltages, and frequencies. Finally, dynamic experiments were conducted using a flow cell and single frequency impedance in order to study continuous and real-time measurements of dopamine.

Bibliography of Soviet Laser Developments, Number 81, January-February 1986

DTIC Science & Technology

1987-04-24

Lasers , Liquid Lasers ; Gas Lasers ; Chemical Lasers , Laser Components Nonlinear Optics, Spectroscopy of Laser Materials, Ultrashort Pulse Generation...spectroscopy of laser materials; ultrashort pulse generation; theoretical aspects of advanced lasers ; and general laser theory. Laser applications are...28 6. Acoustic Interaction ................ 28 G. Spectroscopy of Laser Materials ......... 28 H. Ultrashort

On-chip dual-comb based on quantum cascade laser frequency combs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Villares, G., E-mail: gustavo.villares@phys.ethz.ch; Wolf, J.; Kazakov, D.

2015-12-21

Dual-comb spectroscopy is emerging as an appealing application of mid-infrared frequency combs for high-resolution molecular spectroscopy, as it leverages on the unique coherence properties of frequency combs. Here, we present an on-chip dual-comb source based on mid-infrared quantum cascade laser frequency combs. Control of the combs repetition and offset frequencies is obtained by integrating micro-heaters next to each laser. We show that a full control of the dual-comb system is possible, by measuring a multi-heterodyne beating corresponding to an optical bandwidth of 32 cm{sup −1} centered at 1330 cm{sup −1} (7.52 μm), demonstrating that this device represents a critical step towards compact dual-combmore » systems.« less

Superconducting Nb DHEB Mixer Arrays for Far-Infrared Spectroscopy

NASA Technical Reports Server (NTRS)

Gerecht, E.; Reintsema, C. D.; Grossman, E. N.; Betz, A. L.; Boreiko, R. T.

2001-01-01

We are developing a heterodyne focal plane array with up to eight elements to study lines of the interstellar medium and planetary atmospheres with frequencies of 2 THz and above. Our fabrication process utilizes selective ion milling techniques to produce Nb Diffusion-Cooled Hot Electron Bolometric (DHEB) mixers from a bilayer thin film of Au/Nb deposited on a silicon substrate. A micro-bridge of 10 nm thick Nb forms the HEB device. The first generation of devices with lateral dimensions of 100 nm by 80 nm were fabricated at the feed of a broadband spiral antenna with a frequency response designed for up to 16 THz. Harmonic multiplier sources becoming available within the next few years should have sufficient power to provide a local-oscillator source for small-format, quasi-optically coupled arrays of these mixers. First generation devices measured at our laboratory have demonstrated a critical temperature (Tc) of 4.8 K with a 0.5 K transition width. These DHEB mixers are expected to have an optimum operational temperature of 1.8-2.0 K. The current four element array mixer block will ultimately be replaced by a dual polarization slot-ring array configuration with up to eight elements.

Study of ultrasound-assisted radio-frequency plasma discharges in n-dodecane

NASA Astrophysics Data System (ADS)

Camerotto, Elisabeth; De Schepper, Peter; Nikiforov, Anton Y.; Brems, Steven; Shamiryan, Denis; Boullart, Werner; Leys, Christophe; De Gendt, Stefan

2012-10-01

This paper investigates the generation of a stable plasma phase in a liquid hydrocarbon (n-dodecane) by means of ultrasound (US) and radio-frequency (RF) or electromagnetic radiation. It is demonstrated for the first time that ultrasonic aided RF plasma discharges can be generated in a liquid. Plasma discharges are obtained for different gas mixtures at a pressure of 12 kPa and at low ignition powers (100 W for RF and 2.4 W cm-2 for US). Direct carbon deposition from the liquid precursor on Cu, Ni, SiO2 and Si substrates has been obtained and no apparent compositional or structural difference among the substrate materials was observed. Characterization of the deposited solid phase revealed an amorphous structure. In addition, structural changes in the liquid precursor after plasma treatment have been analysed. Optical emission spectroscopy (OES) allowed the estimation of several plasma characteristic temperatures. The plasma excitation temperature was estimated to be about 2.3-2.4 eV. The rotational and vibrational temperatures of the discharge in n-dodecane with Ar as a feed gas were 1400 K and 6500 K, respectively. In Ar/O2 plasma, an increased rotational (1630 K) and vibrational temperature (7200 K) were obtained.

Retrieval of complex χ(2) parts for quantitative analysis of sum-frequency generation intensity spectra

PubMed Central

Hofmann, Matthias J.; Koelsch, Patrick

2015-01-01

Vibrational sum-frequency generation (SFG) spectroscopy has become an established technique for in situ surface analysis. While spectral recording procedures and hardware have been optimized, unique data analysis routines have yet to be established. The SFG intensity is related to probing geometries and properties of the system under investigation such as the absolute square of the second-order susceptibility χ(2)2. A conventional SFG intensity measurement does not grant access to the complex parts of χ(2) unless further assumptions have been made. It is therefore difficult, sometimes impossible, to establish a unique fitting solution for SFG intensity spectra. Recently, interferometric phase-sensitive SFG or heterodyne detection methods have been introduced to measure real and imaginary parts of χ(2) experimentally. Here, we demonstrate that iterative phase-matching between complex spectra retrieved from maximum entropy method analysis and fitting of intensity SFG spectra (iMEMfit) leads to a unique solution for the complex parts of χ(2) and enables quantitative analysis of SFG intensity spectra. A comparison between complex parts retrieved by iMEMfit applied to intensity spectra and phase sensitive experimental data shows excellent agreement between the two methods. PMID:26450297

Small Molecules and Sum Frequency Generation Probes of Nanoparticulate TiO2

NASA Astrophysics Data System (ADS)

Shultz, Mary Jane

2006-03-01

Anatase TiO2 is known to photo catalytically mineralize a wide variety of pollutants and pathogens, both airborne and in aqueous solution. One of the major benefits of basing water treatment systems on TiO2 is that it is environmentally benign and so non toxic that it is used as a colorant in creamy salad dressing. The primary impediment to wide spread implementation of a TiO2 based system for water decontamination is that the quantum efficiency in contact with condense phase water is less than 5%. Since the quantum efficiency for destruction of airborne materials is greater than 80%, the potential for increased efficiency is very real. To convert the potential to practice, the oxidation mechanism needs to be more fully understood. We will report on the results of using a nonlinear optical spectroscopy, sum frequency generation (SFG) as an in situ probe of interactions at the TiO2 surface. Results suggest that the dominant oxidation mechanism converts from a direct to an indirect mechanism as the water content (vapor pressure) increases. This presentation will discuss the probe technique as well as the results.

Two-dimensional vibrational-electronic spectroscopy

NASA Astrophysics Data System (ADS)

Courtney, Trevor L.; Fox, Zachary W.; Slenkamp, Karla M.; Khalil, Munira

2015-10-01

Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (νCN) and either a ligand-to-metal charge transfer transition ([FeIII(CN)6]3- dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN)5FeIICNRuIII(NH3)5]- dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific νCN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.

Two-dimensional vibrational-electronic spectroscopy.

PubMed

Courtney, Trevor L; Fox, Zachary W; Slenkamp, Karla M; Khalil, Munira

2015-10-21

Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (νCN) and either a ligand-to-metal charge transfer transition ([Fe(III)(CN)6](3-) dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN)5Fe(II)CNRu(III)(NH3)5](-) dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific νCN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.

Multi-distance diffuse optical spectroscopy with a single optode via hypotrochoidal scanning.

PubMed

Applegate, Matthew B; Roblyer, Darren

2018-02-15

Frequency-domain diffuse optical spectroscopy (FD-DOS) is an established technique capable of determining optical properties and chromophore concentrations in biological tissue. Most FD-DOS systems use either manually positioned, handheld probes or complex arrays of source and detector fibers to acquire data from many tissue locations, allowing for the generation of 2D or 3D maps of tissue. Here, we present a new method to rapidly acquire a wide range of source-detector (SD) separations by mechanically scanning a single SD pair. The source and detector fibers are mounted on a scan head that traces a hypotrochoidal pattern over the sample that, when coupled with a high-speed FD-DOS system, enables the rapid collection of dozens of SD separations for depth-resolved imaging. We demonstrate that this system has an average error of 4±2.6% in absorption and 2±1.8% in scattering across all SD separations. Additionally, by linearly translating the device, the size and location of an absorbing inhomogeneity can be determined through the generation of B-scan images in a manner conceptually analogous to ultrasound imaging. This work demonstrates the potential of single optode diffuse optical scanning for depth resolved visualization of heterogeneous biological tissues at near real-time rates.

A Dicobalt Complex with an Unsymmetrical Quinonoid Bridge Isolated in Three Units of Charge: A Combined Structural, (Spectro)electrochemical, Magnetic and Spectroscopic Study.

PubMed

van der Meer, Margarethe; Rechkemmer, Yvonne; Frank, Uta; Breitgoff, Frauke D; Hohloch, Stephan; Su, Cheng-Yong; Neugebauer, Petr; Marx, Raphael; Dörfel, María; van Slageren, Joris; Sarkar, Biprajit

2016-09-19

Quinonoid ligands are excellent bridges for generating redox-rich dinuclear assemblies. A large majority of these bridges are symmetrically substituted, with examples of unsymmetrically substituted quinonoid bridges being extremely rare. We present here a dicobalt complex in its various redox states with an unsymmetrically substituted quinonoid bridging ligand. Two homovalent forms and one mixed-valent form have been isolated and characterized by single crystal X-ray diffraction. The complex displays a large comproportionation constant for the mixed-valent state which is three orders of magnitude higher than that observed for the analogous complex with a symmetrically substituted bridge. Results from electrochemistry, UV/Vis/NIR spectroelectrochemistry, SQUID magnetometry, multi-frequency EPR spectroscopy and FIR spectroscopy are used to probe the electronic structures of these complexes. FIR provides direct evidence of exchange coupling. The results presented here display the advantages of using an unsymmetrically substituted bridge: site specific redox chemistry, high thermodynamic stabilization of the mixed-valent form, isolation and crystallization of various redox forms of the complex. This work represents an important step on the way to generating heterodinuclear complexes for use in cooperative catalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relaxor ferroelectricity, ferromagnetic and optical second harmonic properties in lanthanum lithium niobate (La0.05Li0.85NbO3) nanoparticles

NASA Astrophysics Data System (ADS)

Díaz-Moreno, Carlos A.; Ding, Yu; Li, Chunqiang; Portelles, Jorge; Heiras, J.; Hurtado-Macias, A.; Farias, J. R.; González-Hernández, J.; Yacamán, M. J.; López, Jorge

2017-07-01

Relaxor ferroelectricity, ferromagnetism and Second Harmonic Generation properties were founded and studied as a function of a reduction heat treatment at 650 °C in a Ar-5%H2 atmosphere in stoichiometric La0.05Li0.85NbO3 nanoparticles of 40 nm. A diffuse dielectric anomaly related with relaxor behavior from 25 °C to 800 °C in a frequency range from 100 Hz to 1 MHz was founded. It also shows ferromagnetic anhysterestic type and ferroelectric hysteresis loops at room temperature with a magnetic spin remnant of 2.5 × 10-3 emu/g and polarization saturation of 0.235 μC/cm2, remnant polarization of 0.141 μC/cm2, coercive field of 1.35 kV/cm, respectively. It shows very good second harmonic generation signal at 450 nm and 500 nm. High Resolution Transmission Electron Microscopy, X-ray Photoelectron Spectroscopy and Raman spectroscopy, indicate an ABO3 perovskite structure, new electronic binding energy structure for La (5s, 4d), Li (1s), Nb (4s, 3d, 4p) and oxygen (1s, 2s) and new vibrations modes on octahedron NbO6 related to multiferroic single phase nanoparticles, respectively.

Diamondoid synthesis in atmospheric pressure adamantane-argon-methane-hydrogen mixtures using a continuous flow plasma microreactor

NASA Astrophysics Data System (ADS)

Stauss, Sven; Ishii, Chikako; Pai, David Z.; Urabe, Keiichiro; Terashima, Kazuo

2014-06-01

Due to their small size, low-power consumption and potential for integration with other devices, microplasmas have been used increasingly for the synthesis of nanomaterials. Here, we have investigated the possibility of using dielectric barrier discharges generated in continuous flow glass microreactors for the synthesis of diamondoids, at temperatures of 300 and 320 K, and applied voltages of 3.2-4.3 kVp-p, at a frequency of 10 kHz. The microplasmas were generated in gas mixtures containing argon, methane, hydrogen and adamantane, which was used as a precursor and seed. The plasmas were monitored by optical emission spectroscopy measurements and the synthesized products were characterized by gas chromatography—mass spectrometry (GC-MS). Depending on the gas composition, the optical emission spectra contained CH and C2 bands of varying intensities. The GC-MS measurements revealed that diamantane can be synthesized by microplasmas generated at atmospheric pressure, and that the yields highly depend on the gas composition and the presence of carbon sources.

Flame extinction limit and particulates formation in fuel blends

NASA Astrophysics Data System (ADS)

Subramanya, Mahesh

Many fuels used in material processing and power generation applications are generally a blend of various hydrocarbons. Although the combustion and aerosol formation dynamics of individual fuels is well understood, the flame dynamics of fuel blends are yet to be characterized. This research uses a twin flame counterflow burner to measure flame velocity, flame extinction, particulate formation and particulate morphology of hydrogen fuel blend flames at different H2 concentration, oscillation frequencies and stretch conditions. Phase resolved spectroscopic measurements (emission spectra) of OH, H, O and CH radical/atom concentrations is used to characterize the heat release processes of the flame. In addition flame generated particulates are collected using thermophoretic sample technique and are qualitative analyzed using Raman Spectroscopy and SEM. Such measurements are essential for the development of advanced computational tools capable of predicting fuel blend flame characteristics at realistic combustor conditions. The data generated through the measurements of this research are representative, and yet accurate, with unique well defined boundary conditions which can be reproduced in numerical computations for kinetic code validations.

Efficient and broadband Stokes wave generation by degenerate four-wave mixing at the mid-infrared wavelength in a silica photonic crystal fiber.

PubMed

Yuan, Jinhui; Sang, Xinzhu; Wu, Qiang; Zhou, Guiyao; Yu, Chongxiu; Wang, Kuiru; Yan, Binbin; Han, Ying; Farrell, Gerald; Hou, Lantian

2013-12-15

Based on degenerate four-wave mixing (FWM), the broadband Stokes waves are efficiently generated at the mid-infrared wavelength above 2 μm, for the first time to our knowledge, by coupling the femtosecond pulses into the fundamental mode of a silica photonic crystal fiber designed and fabricated in our laboratory. Influences of the power and wavelength of pump pulses on the phase-matched frequency conversion process are discussed. When pump pulses with central wavelength of 815 nm and average power of 300 mW are used, the output power ratio of the Stokes wave generated at 2226 nm and the residual pump wave P(s)/P(res) is estimated to be 10.8:1, and the corresponding conversion efficiency η(s) and bandwidth B(s) of the Stokes wave can be up to 26% and 33 nm, respectively. The efficient and broadband Stokes waves can be used as the ultrashort pulse sources for mid-infrared photonics and spectroscopy.

Time-resolved study of formate on Ni( 1 1 1 ) by picosecond SFG spectroscopy

NASA Astrophysics Data System (ADS)

Kusafuka, K.; Noguchi, H.; Onda, K.; Kubota, J.; Domen, K.; Hirose, C.; Wada, A.

2002-04-01

Time-resolved vibrational measurements were carried out on formate (HCOO) adsorbed on Ni(1 1 1) surface by combining the sum-frequency generation method and picosecond laser system (time resolution of 6 ps). Rapid intensity decrease (within the time resolution) followed by intensity recovery (time constant of several tens of ps) of CH stretching signal was observed when picosecond 800 nm pulse was irradiated on the sample surface. From the results of temperature and pump fluence dependences of temporal behaviour of signal intensity, we concluded that the observed intensity change was induced by non-thermal process. Mechanism of the temporal intensity change was discussed.

The Er3+-Yb3+ codoped La2O3 phosphor in finger print detection and optical heating.

PubMed

Dey, Riya; Pandey, Anurag; Rai, Vineet Kumar

2014-07-15

The presence of impurities and morphological information about the Er(3+)-Yb(3+) codoped La2O3 phosphors prepared by two different synthesis techniques have been obtained with the help of Fourier transform infrared (FTIR) spectroscopy and Scanning electron microscopy (SEM) respectively. The effect of synthesis process on the frequency upconversion (UC) emission with an excitation at 980 nm from laser diode radiation has been performed. The use of codoped phosphor in latent finger print detection and laser induced heat generation has also been explored. Copyright © 2014 Elsevier B.V. All rights reserved.

New sample cell configuration for wide-frequency dielectric spectroscopy: DC to radio frequencies.

PubMed

Nakanishi, Masahiro; Sasaki, Yasutaka; Nozaki, Ryusuke

2010-12-01

A new configuration for the sample cell to be used in broadband dielectric spectroscopy is presented. A coaxial structure with a parallel plate capacitor (outward parallel plate cell: OPPC) has made it possible to extend the frequency range significantly in comparison with the frequency range of the conventional configuration. In the proposed configuration, stray inductance is significantly decreased; consequently, the upper bound of the frequency range is improved by two orders of magnitude from the upper limit of conventional parallel plate capacitor (1 MHz). Furthermore, the value of capacitance is kept high by using a parallel plate configuration. Therefore, the precision of the capacitance measurement in the lower frequency range remains sufficiently high. Finally, OPPC can cover a wide frequency range (100 Hz-1 GHz) with an appropriate admittance measuring apparatus such as an impedance or network analyzer. The OPPC and the conventional dielectric cell are compared by examining the frequency dependence of the complex permittivity for several polar liquids and polymeric films.

Generation of sub-two-cycle millijoule infrared pulses in an optical parametric chirped-pulse amplifier and their application to soft x-ray absorption spectroscopy with high-flux high harmonics

NASA Astrophysics Data System (ADS)

Ishii, Nobuhisa; Kaneshima, Keisuke; Kanai, Teruto; Watanabe, Shuntaro; Itatani, Jiro

2018-01-01

An optical parametric chirped-pulse amplifier (OPCPA) based on bismuth triborate (BiB3O6, BIBO) crystals has been developed to deliver 1.5 mJ, 10.1 fs optical pulses around 1.6 μm with a repetition rate of 1 kHz and a stable carrier-envelope phase. The seed and pump pulses of the BIBO-based OPCPA are provided from two Ti:sapphire chirped-pulse amplification (CPA) systems. In both CPA systems, transmission gratings are used in the stretchers and compressors that result in a high throughput and robust operation without causing any thermal problem and optical damage. The seed pulses of the OPCPA are generated by intrapulse frequency mixing of a spectrally broadened continuum, temporally stretched to approximately 5 ps then, and amplified to more than 1.5 mJ. The amplified pulses are compressed in a fused silica block down to 10.1 fs. This BIBO-based OPCPA has been applied to high-flux high harmonic generation beyond the carbon K edge at 284 eV. The high-flux soft-x-ray continuum allows measuring the x-ray absorption near-edge structure of the carbon K edge within 2 min, which is shorter than a typical measurement time using synchrotron-based light sources. This laser-based table-top soft-x-ray source is a promising candidate for ultrafast soft x-ray spectroscopy with femtosecond to attosecond time resolution.

Quantum-enhanced spectroscopy with entangled multiphoton states

NASA Astrophysics Data System (ADS)

Dinani, Hossein T.; Gupta, Manish K.; Dowling, Jonathan P.; Berry, Dominic W.

2016-06-01

Traditionally, spectroscopy is performed by examining the position of absorption lines. However, at frequencies near the transition frequency, additional information can be obtained from the phase shift. In this work we consider the information about the transition frequency obtained from both the absorption and the phase shift, as quantified by the Fisher information in an interferometric measurement. We examine the use of multiple single-photon states, NOON states, and numerically optimized states that are entangled and have multiple photons. We find the optimized states that improve over the standard quantum limit set by independent single photons for some atom number densities.

Antenna design for propagating spin wave spectroscopy in ferromagnetic thin films

NASA Astrophysics Data System (ADS)

Zhang, Yan; Yu, Ting; Chen, Ji-lei; Zhang, You-guang; Feng, Jian; Tu, Sa; Yu, Haiming

2018-03-01

In this paper, we investigate the characteristics of antenna for propagating-spin-wave-spectroscopy (PSWS) experiment in ferromagnetic thin films. Firstly, we simulate the amplitude and phase distribution of the high-frequency magnetic field around antenna by high frequency structure simulator (HFSS). And then k distribution of the antenna is obtained by fast Fourier transformation (FFT). Furthermore, three kinds of antenna designs, i.e. micro-strip line, coplanar waveguide (CPW), loop, are studied and compared. How the dimension parameter of antenna influence the corresponding high-frequency magnetic field amplitude and k distribution are investigated in details.