APPLICATION OF JET REMPI AND LIBS TO AIR TOXIC MONITORING

EPA Science Inventory

The paper discusses three advanced, laser-based monitoring techniques that the EPA is assisting in developing for real time measurement of toxic aerosol compounds. One of the three techniques is jet resonance enhanced multiphoton ionization (Jet REMPI) coupled with a time-of-flig...

WAVELENGTH-RESOLVED REMPI MASS SPECTROMETRY FOR THE MONITORING OF TOXIC INCINERATION TRACE GASES

EPA Science Inventory

Structure-selective measurement techniques are needed for the assessment of the toxic loading of incinerator gases. This review article shows that wavelength-resolved, resonance-enhanced, multiphoton- ionization (REMPY) mass spectrometry can be used to this end. In this case, how...

Ionic rotational branching ratios in resonant enhanced multiphoton ionization of NO via the A2Sigma(+)(3s sigma) and D2Sigma(+)(3p sigma) states

NASA Technical Reports Server (NTRS)

Rudolph, H.; Mckoy, V.; Dixit, S. N.; Huo, W. M.

1988-01-01

Results are presented for the rotationally resolved photoelectron spectra resulting from a (2 + 1) one-color resonant enhanced multiphoton ionization (REMPI) of NO via the rotationally clean S21(11.5) and mixed S11(15.5) + R21(15.5) branches of the 0-0 transition in the D-X band. The calculations were done in the fixed-nuclei frozen core approximation. The resulting photoionization spectra, convoluted with a Lorentzian detection function, agree qualitatively with experimental results of Viswanathan et al. (1986) and support their conclusion that the nonspherical nature of the molecular potential creates a substantial l-mixing in the continuum, which in turn leads to the intense Delta N = 0 peak. The rather strong photoelectron energy dependence of the rotational branching ratios of the D 2Sigma(+) S21(11.5) line was investigated and compared to the weak energy dependence of the A 2Sigma(+) R22(21.5) line.

Spatially resolved measurement of singlet delta oxygen by radar resonance-enhanced multiphoton ionization.

PubMed

Wu, Yue; Zhang, Zhili; Ombrello, Timothy M

2013-07-01

Coherent microwave Rayleigh scattering (Radar) from resonance-enhanced multiphoton ionization (REMPI) was demonstrated to directly and nonintrusively measure singlet delta oxygen, O(2)(a(1)Δ(g)), with high spatial resolution. Two different approaches, photodissociation of ozone and microwave discharge plasma in an argon and oxygen flow, were utilized for O(2)(a(1)Δ(g)) generation. The d(1)Π(g)←a(1)Δ(g) (3-0) and d(1)Π(g)←a(1)Δ(g) (1-0) bands of O(2)(a(1)Δ(g)) were detected by Radar REMPI for two different flow conditions. Quantitative absorption measurements using sensitive off-axis integrated cavity output spectroscopy (ICOS) was used simultaneously to evaluate the accuracy and sensitivity of the Radar REMPI technique. The detection limit of Radar REMPI was found to be comparable to the ICOS technique with a detection threshold of approximately 10(14) molecules/cm(3) but with a spatial resolution that was 8 orders of magnitude smaller than the ICOS technique.

DEVELOPMENT OF A JET-REMPI (RESONANTLY ENHANCED MULTIPHOTON IONIZATION) CONTINUOUS MONITOR FOR ENVIRONMENTAL APPLICATIONS. (R827927)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Monitoring of Hazardous Air Pollutant Surrogates Using Resonance Enhanced Multiphoton Ionization/Time of Flight Mass Spectrometry

EPA Science Inventory

EPA’s preferred approach for regulatory emissions compliance is based upon real-time monitoring of individual hazardous air pollutants (HAPs). Real-time, continuous monitoring not only provides the most comprehensive assurance of emissions compliance, but also can serve as...

Resonance Enhanced Multi-Photon Ionization and Uv-Uv Hole-Burning Spectroscopic Studies of Jet-Cooled Acetanilide Derivatives

NASA Astrophysics Data System (ADS)

Moon, Ceol Joo; Min, Ahreum; Ahn, Ahreum; Lee, Seung Jun; Choi, Myong Yong; Kim, Seong Keun

2013-06-01

Conformational investigations and photochemistry of jet-cooled methacetine (MA) and phenacetine (PA) using one color resonant two-photon ionization (REMPI), UV-UV hole-burning and IR-dip spectroscopy are presented. MA and PA are derivatives of acetanilide, substituted by methoxyl, ethoxyl group in the para position of acetanilide, respectively. Moreover, we have investigated conformational information of the acetanilide derivatives (AAP, MA and PA)-water. In this work, we will present and discuss the solvent effects of the hydroxyl group of acetanilide derivatives in the excited state.

Measurements of trap dynamics of cold OH molecules using resonance-enhanced multiphoton ionization

NASA Astrophysics Data System (ADS)

Gray, John M.; Bossert, Jason A.; Shyur, Yomay; Lewandowski, H. J.

2017-08-01

Trapping cold, chemically important molecules with electromagnetic fields is a useful technique to study small molecules and their interactions. Traps provide long interaction times, which are needed to precisely examine these low-density molecular samples. However, the trapping fields lead to nonuniform molecular density distributions in these systems. Therefore, it is important to be able to experimentally characterize the spatial density distribution in the trap. Ionizing molecules at different locations in the trap using resonance-enhanced multiphoton ionization (REMPI) and detecting the resulting ions can be used to probe the density distribution even at the low density present in these experiments because of the extremely high efficiency of detection. Until recently, one of the most chemically important molecules, OH, did not have a convenient REMPI scheme identified. Here, we use a newly developed 1 +1' REMPI scheme to detect trapped cold OH molecules. We use this capability to measure the trap dynamics of the central density of the cloud and the density distribution. These types of measurements can be used to optimize loading of molecules into traps, as well as to help characterize the energy distribution, which is critical knowledge for interpreting molecular collision experiments.

A velocity-map imaging study of methyl non-resonant multiphoton ionization from the photodissociation of CH3I in the A-band

PubMed Central

Poullain, Sonia Marggi; Chicharro, David V.; Rubio-Lago, Luis; García-Vela, Alberto

2017-01-01

Chemical reaction dynamics and, particularly, photodissociation in the gas phase are generally studied using pump–probe schemes where a first laser pulse induces the process under study and a second one detects the produced fragments. Providing an efficient detection of ro-vibrationally state-selected photofragments, the resonance enhanced multiphoton ionization (REMPI) technique is, without question, the most popular approach used for the probe step, while non-resonant multiphoton ionization (NRMPI) detection of the products is scarce. The main goal of this work is to test the sensitivity of the NRMPI technique to fragment vibrational distributions arising from molecular photodissociation processes. We revisit the well-known process of methyl iodide photodissociation in the A-band at around 280 nm, using the velocity-map imaging technique in conjunction with NRMPI of the methyl fragment. The detection wavelength, carefully selected to avoid any REMPI transition, was scanned between 325 and 335 nm seeking correlations between the different observables—the product vibrational, translational and angular distributions—and the excitation wavelength of the probe laser pulse. The experimental results have been discussed on the base of quantum dynamics calculations of photofragment vibrational populations carried out on available ab initio potential-energy surfaces using a four-dimensional model. This article is part of the themed issue ‘Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces’. PMID:28320907

Spectroscopic study of N2(b1Πu, ν = 8) by atmospheric-pressure resonant-enhanced multiphoton ionization and fluorescence detection.

PubMed

Adams, Steven F; Williamson, James M

2013-12-19

A spectroscopic analysis of the strongly perturbed N2(b(1)Πu, ν = 8) state has been conducted, accounting for b(1)Πu(ν = 8) ← X (1)Σg(+)(ν = 0) transitions, for the first time, up to J' = 20. A novel laser spectroscopy technique, using a combination of resonant-enhanced multiphoton ionization and fluorescence detection at atmospheric pressure, avoids the severe effects of perturbation reported in past extreme vacuum ultraviolet absorption experiments that produced weak and unusable spectra for the ν = 8 level. The R, Q, and P branches of the three-photon absorption transition b(1)Πu(ν = 8) ← X(1)Σg(+)(ν = 0) were fit, allowing rotational term energy assignment up to J' = 20 and molecular constants to be determined. Evidence of the previously suspected perturbation in b(1)Πu(ν = 8) is clear in this data, with significant Λ-type doubling at higher J' along with an anomalous negative value determined for the centrifugal distortion coefficient.

Resonant- and avalanche-ionization amplification of laser-induced plasma in air

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

Wu, Yue; Zhang, Zhili, E-mail: zzhang24@utk.edu; Jiang, Naibo

2014-10-14

Amplification of laser-induced plasma in air is demonstrated utilizing resonant laser ionization and avalanche ionization. Molecular oxygen in air is ionized by a low-energy laser pulse employing (2 + 1) resonance-enhanced multi-photon ionization (REMPI) to generate seed electrons. Subsequent avalanche ionization of molecular oxygen and nitrogen significantly amplifies the laser-induced plasma. In this plasma-amplification effect, three-body attachments to molecular oxygen dominate the electron-generation and -loss processes, while either nitrogen or argon acts as the third body with low electron affinity. Contour maps of the electron density within the plasma obtained in O₂/N₂ and O₂/Ar gas mixtures are provided to showmore » relative degrees of plasma amplification with respect to gas pressure and to verify that the seed electrons generated by O₂ 2 + 1 REMPI are selectively amplified by avalanche ionization of molecular nitrogen in a relatively low-pressure condition (≤100 Torr). Such plasma amplification occurring in air could be useful in aerospace applications at high altitude.« less

REAL-TIME EMISSION CHARACTERIZATION OF ORGANIC AIR TOXIC POLLUTANTS DURING STEADY STATE AND TRANSIENT OPERATION OF A MEDIUM DUTY DIESEL ENGINE

EPA Science Inventory

An on-line monitoring method, jet resonance-enhanced multi-photon ionization (REMPI) with time-of-flight mass spectrometry (TOFMS) was used to measure emissions of organic air toxics from a medium-duty (60 kW)diesel generator during transient and steady state operations. Emission...

Non-volatile analysis in fruits by laser resonant ionization spectrometry: application to resveratrol (3,5,4'-trihydroxystilbene) in grapes

NASA Astrophysics Data System (ADS)

Montero, C.; Orea, J. M.; Soledad Muñoz, M.; Lobo, R. F. M.; González Ureña, A.

A laser desorption (LD) coupled with resonance-enhanced multiphoton ionisation (REMPI) and time-of-flight mass spectrometry (TOFMS) technique for non-volatile trace analysis compounds is presented. Essential features are: (a) an enhanced desorption yield due to the mixing of metal powder with the analyte in the sample preparation, (b) a high resolution, great sensitivity and low detection limit due to laser resonant ionisation and mass spectrometry detection. Application to resveratrol content in grapes demonstrated the capability of the analytical method with a sensitivity of 0.2 pg per single laser shot and a detection limit of 5 ppb.

UV and VUV spectroscopy and photochemistry of small molecules in a supersonic jet

NASA Technical Reports Server (NTRS)

Ruehl, E.; Vaida, V.

1990-01-01

UV and VUV absorption and emission spectroscopy is used to probe jet cooled molecules, free radicals, and clusters in the gas phase. Due to efficient cooling inhomogeneous effects on spectral line widths are eliminated. Therefore from these spectra, both structural and dynamical information is obtained. The photoproducts of these reactions are probed by resonance enhanced multiphoton ionization.

Study on the decomposition of trace benzene over V2O5-WO3/TiO2-based catalysts in simulated flue gas

EPA Science Inventory

Commercial and laboratory-prepared V2O5–WO3/TiO2-based catalysts with different compositions were tested for catalytic decomposition of chlorobenzene （ClBz） in simulated flue gas. Resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) was employe...

Supramolecular clusters between carbohydrates and concave pyridines. Detection in the gas phase by resonance-enhanced multi-photon ionization reflectron time-of-flight mass spectrometer.

PubMed

Liebig, Timo; Lüning, Ulrich; Grotemeyer, Jürgen

2006-01-01

For the first time the formation of supramolecular clusters between concave pyridines and different carbohydrates could be observed in the gas phase. The different clusters have been investigated by means of laser desorption into a supersonic beam followed by resonant multi photon excitation yielding mass spectra with high intensity of the different cluster. These preliminary results open a way for the investigations of the hydrogen bonds in these compounds.

Photoelectron circular dichroism of bicyclic ketones from multiphoton ionization with femtosecond laser pulses.

PubMed

Lux, Christian; Wollenhaupt, Matthias; Sarpe, Cristian; Baumert, Thomas

2015-01-12

Photoelectron circular dichroism (PECD) is a CD effect up to the ten-percent regime and shows contributions from higher-order Legendre polynomials when multiphoton ionization is compared to single-photon ionization. We give a full account of our experimental methodology for measuring the multiphoton PECD and derive quantitative measures that we apply on camphor, fenchone and norcamphor. Different modulations and amplitudes of the contributing Legendre polynomials are observed despite the similarity in chemical structure. In addition, we study PECD for elliptically polarized light employing tomographic reconstruction methods. Intensity studies reveal dissociative ionization as the origin of the observed PECD effect, whereas ionization of the intermediate resonance is dominating the signal. As a perspective, we suggest to make use of our tomographic data as an experimental basis for a complete photoionization experiment and give a prospect of PECD as an analytic tool. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoionization pathways and thresholds in generation of Lyman-α radiation by resonant four-wave mixing in Kr-Ar mixture

NASA Astrophysics Data System (ADS)

Louchev, Oleg A.; Saito, Norihito; Oishi, Yu; Miyazaki, Koji; Okamura, Kotaro; Nakamura, Jumpei; Iwasaki, Masahiko; Wada, Satoshi

2016-09-01

We develop a set of analytical approximations for the estimation of the combined effect of various photoionization processes involved in the resonant four-wave mixing generation of ns pulsed Lyman-α (L-α ) radiation by using 212.556 nm and 820-845 nm laser radiation pulses in Kr-Ar mixture: (i) multi-photon ionization, (ii) step-wise (2+1)-photon ionization via the resonant 2-photon excitation of Kr followed by 1-photon ionization and (iii) laser-induced avalanche ionization produced by generated free electrons. Developed expressions validated by order of magnitude estimations and available experimental data allow us to identify the area for the operation under high input laser intensities avoiding the onset of full-scale discharge, loss of efficiency and inhibition of generated L-α radiation. Calculations made reveal an opportunity for scaling up the output energy of the experimentally generated pulsed L-α radiation without significant enhancement of photoionization.

Photoelectron circular dichroism in different ionization regimes

NASA Astrophysics Data System (ADS)

Wollenhaupt, Matthias

2016-12-01

Photoelectron circular dichroism (PECD) describes an asymmetry in the photoelectron angular distribution (PAD) from photoionization of randomly oriented enantiomers with circularly polarized light. Beaulieu et al present a comprehensive set of measured PADs from multiphoton ionization of limonene and fenchone in different ionization regimes (multiphoton and tunneling) and analyze the resulting PECD (Beaulieu et al 2016 New J. Phys. 18 102002). From their observations the authors conclude that the PECD is universal in the sense that the molecular chirality is encoded in the PAD independent of the ionization regime. The analysis is supplemented by a classical model based on electron scattering in a chiral potential. The paper presents beautiful data and is an important step towards a more complete physical picture of PECD. The results and their interpretation stimulate the ongoing vivid debate on the role of resonances in multiphoton PECD.

Multi-photon ionization of atoms in intense short-wavelength radiation fields

NASA Astrophysics Data System (ADS)

Meyer, Michael

2015-05-01

The unprecedented characteristics of XUV and X-ray Free Electron Lasers (FELs) have stimulated numerous investigations focusing on the detailed understanding of fundamental photon-matter interactions in atoms and molecules. In particular, the high intensities (up to 106 W/cm2) giving rise to non-linear phenomena in the short wavelength regime. The basic phenomenology involves the production of highly charged ions via electron emission to which both sequential and direct multi-photon absorption processes contribute. The detailed investigation of the role and relative weight of these processes under different conditions (wavelength, pulse duration, intensity) is the key element for a comprehensive understanding of the ionization dynamics. Here the results of recent investigations are presented, performed at the FELs in Hamburg (FLASH) and Trieste (FERMI) on atomic systems with electronic structures of increasing complexity (Ar, Ne and Xe). Mainly, electron spectroscopy is used to obtain quantitative information about the relevance of various multi-photon ionization processes. For the case of Ar, a variety of processes including above threshold ionization (ATI) from 3p and 3s valence shells, direct 2p two-photon ionization and resonant 2p-4p two-photon excitations were observed and their role was quantitatively determined comparing the experimental ionization yields to ab-initio calculations of the cross sections for the multi-photon processes. Using Ar as a benchmark to prove the reliability of the combined experimental and theoretical approach, the more complex and intriguing case of Xe was studied. Especially, the analysis of the two-photon ATI from the Xe 4d shell reveals new insight into the character of the 4d giant resonance, which was unresolved in the linear one-photon regime. Finally, the influence of intense XUV radiation to the relaxation dynamics of the Ne 2s-3p resonance was investigated by angle-resolved electron spectroscopy, especially be observing the intensity dependent variation of the angular distribution patterns for the sequential ionization process.

Evaluating the Aging of Multiple Emulsions Using Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry.

PubMed

Tsuda, Yukihiro; Uchimura, Tomohiro

2016-01-01

Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry was applied to measurements of multiple emulsions with no pretreatment; a method for the quantitative evaluation of aging was proposed. We prepared water-in-oil-in-water (W/O/W) multiple emulsions containing toluene and m-phenylenediamine. The samples were measured immediately following both preparation and after having been stirred for 24 h. Time profiles of the peak areas for each analyte species were obtained, and several intense spikes for toluene could be detected from each sample after stirring, which suggests that the concentration of toluene in the middle phase had increased during stirring. On the other hand, in the case of a W/O/W multiple emulsion containing phenol and m-phenylenediamine, spikes for m-phenylenediamine, rather than phenol, were detected after stirring. In the present study, the time-profile data were converted into a scatter plot in order to quantitatively evaluate the aging. As a result, the ratio of the plots where strong signal intensities of toluene were detected increased from 8.4% before stirring to 33.2% after stirring for 24 h. The present method could be a powerful tool for evaluating multiple emulsions, such as studies on the kinetics of the encapsulation and release of active ingredients.

Molecular symmetry group analysis of the low-wavenumber torsions and vibration-torsions in the S1 state and ground state cation of p-xylene: An investigation using resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Tuttle, William D.; Groner, Peter; Wright, Timothy G.

2017-03-01

For the first time, a molecular symmetry group (MSG) analysis has been undertaken in the investigation of the electronic spectroscopy of p-xylene (p-dimethylbenzene). Torsional and vibration-torsional (vibtor) levels in the S1 state and ground state of the cation of p-xylene are investigated using resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy. In the present work, we concentrate on the 0-350 cm-1 region, where there are a number of torsional and vibtor bands and we discuss the assignment of this region. In Paper II [W. D. Tuttle et al., J. Chem. Phys. 146, 124309 (2017)], we examine the 350-600 cm-1 region where vibtor levels are observed as part of a Fermi resonance. The similarity of much of the observed spectral activity to that in the related substituted benzenes, toluene and para-fluorotoluene, is striking, despite the different symmetries. The discussion necessitates a consideration of the MSG of p-xylene, which has been designated G72, but we shall also designate [{3,3}]D2h and we include the symmetry operations, character table, and direct product table for this. We also discuss the symmetries of the internal rotor (torsional) levels and the selection rules for the particular electronic transition of p-xylene investigated here.

Measurement of plasma decay processes in mixture of sodium and argon by coherent microwave scattering

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

Zhang Zhili; Shneider, Mikhail N.

2010-03-15

This paper presents the experimental measurement and computational model of sodium plasma decay processes in mixture of sodium and argon by using radar resonance-enhanced multiphoton ionization (REMPI), coherent microwave Rayleigh scattering of REMPI. A single laser beam resonantly ionizes the sodium atoms by means of 2+1 REMPI process. The laser beam can only generate the ionization of the sodium atoms and have negligible ionization of argon. Coherent microwave scattering in situ measures the total electron number in the laser-induced plasma. Since the sodium ions decay by recombination with electrons, microwave scattering directly measures the plasma decay processes of the sodiummore » ions. A theoretical plasma dynamic model, including REMPI of the sodium and electron avalanche ionization (EAI) of sodium and argon in the gas mixture, has been developed. It confirms that the EAI of argon is several orders of magnitude lower than the REMPI of sodium. The theoretical prediction made for the plasma decay process of sodium plasma in the mixture matches the experimental measurement.« less

Cold Multiphoton Matrix Assisted Laser Desorption/Ionization (MALDI)

NASA Astrophysics Data System (ADS)

Harris, Peter; Cooke, William; Tracy, Eugene

2008-05-01

We present evidence of a cold multiphoton MALDI process occurring at a Room Temperature Ionic Liquid (RTIL)/metal interface. Our RTIL, 1-Butyl-3-methylimidazolium hexafluorophosphate, remains a stable liquid at room temperatures, even at pressures lower than 10-9 torr. We focus the 2^nd harmonic of a pulsed (2ns pulse length) Nd:YAG laser onto a gold grid coated with RTIL to generate a cold (narrow velocity spread) ion source with temporal resolution comparable to current MALDI ion sources. Unlike conventional MALDI, we believe multiphoton MALDI does not rely on collisional ionization within the ejection plume, and thus produces large signals at laser intensities just above threshold. Removing the collisional ionization process allow us to eject material from smaller regions of a sample, enhancing the suitability of multiphoton MALDI as an ion imaging technique.

REMPI detection of singlet oxygen 1O2 arising from UV-photodissociation of van der Waals complex isoprene-oxygen C5H8-O2

NASA Astrophysics Data System (ADS)

Bogomolov, Alexandr S.; Dozmorov, Nikolay V.; Kochubei, Sergei A.; Baklanov, Alexey V.

2018-01-01

The one-laser two-color resonance enhanced multiphoton ionization REMPI [(1 + 1‧) + 1] and velocity map imaging have been applied to investigate formation of molecular oxygen in excited singlet O2(a1Δg) and ground O2(X3Σg-) states in the photodissociation of van der Waals complex isoprene-oxygen C5H8-O2. These molecules were found to appear in the different rotational states with translational energy varied from a value as low as ∼1 meV to a distribution with temperature of about 940 K. The observed traces of electron recoil in the images of photoions reveal participation of several ionization pathways of the resonantly excited intermediate states of O2.

Resonance-enhanced multiphoton ionization (REMPI) spectroscopy of bromobenzene and its perdeuterated isotopologue: Assignment of the vibrations of the S{sub 0}, S{sub 1}, and D{sub 0}{sup +} states of bromobenzene and the S{sub 0} and D{sub 0}{sup +} states of iodobenzene

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

Andrejeva, Anna; Tuttle, William D.; Harris, Joe P.

2015-12-28

We report vibrationally resolved spectra of the S{sub 1}←S{sub 0} transition of bromobenzene using resonance-enhanced multiphoton ionization spectroscopy. We study bromobenzene-h{sub 5} as well as its perdeuterated isotopologue, bromobenzene-d{sub 5}. The form of the vibrational modes between the isotopologues and also between the S{sub 0} and S{sub 1} electronic states is discussed for each species, allowing assignment of the bands to be achieved and the activity between states and isotopologues to be established. Vibrational bands are assigned utilizing quantum chemical calculations, previous experimental results, and isotopic shifts. Previous work and assignments of the S{sub 1} spectra are discussed. Additionally, themore » vibrations in the ground state cation, D{sub 0}{sup +}, are considered, since these have also been used by previous workers in assigning the excited neutral state spectra. We also examine the vibrations of iodobenzene in the S{sub 0} and D{sub 0}{sup +} states and comment on the previous assignments of these. In summary, we have been able to assign the corresponding vibrations across the whole monohalobenzene series of molecules, in the S{sub 0}, S{sub 1}, and D{sub 0}{sup +} states, gaining insight into vibrational activity and vibrational couplings.« less

Collective Autoionization in Multiply-Excited Systems: A novel ionization process observed in Helium Nanodroplets

PubMed Central

LaForge, A. C.; Drabbels, M.; Brauer, N. B.; Coreno, M.; Devetta, M.; Di Fraia, M.; Finetti, P.; Grazioli, C.; Katzy, R.; Lyamayev, V.; Mazza, T.; Mudrich, M.; O'Keeffe, P.; Ovcharenko, Y.; Piseri, P.; Plekan, O.; Prince, K. C.; Richter, R.; Stranges, S.; Callegari, C.; Möller, T.; Stienkemeier, F.

2014-01-01

Free electron lasers (FELs) offer the unprecedented capability to study reaction dynamics and image the structure of complex systems. When multiple photons are absorbed in complex systems, a plasma-like state is formed where many atoms are ionized on a femtosecond timescale. If multiphoton absorption is resonantly-enhanced, the system becomes electronically-excited prior to plasma formation, with subsequent decay paths which have been scarcely investigated to date. Here, we show using helium nanodroplets as an example that these systems can decay by a new type of process, named collective autoionization. In addition, we show that this process is surprisingly efficient, leading to ion abundances much greater than that of direct single-photon ionization. This novel collective ionization process is expected to be important in many other complex systems, e.g. macromolecules and nanoparticles, exposed to high intensity radiation fields. PMID:24406316

Production of a beam of highly vibrationally excited CO using perturbations.

PubMed

Bartels, Nils; Schäfer, Tim; Hühnert, Jens; Field, Robert W; Wodtke, Alec M

2012-06-07

An intense molecular beam of CO (X(1)Σ(+)) in high vibrational states (v = 17, 18) was produced by a new approach that we call PUMP - PUMP - PERTURB and DUMP. The basic idea is to access high vibrational states of CO e(3)Σ(-) via a two-photon doubly resonant transition that is perturbed by the A(1)Π state. DUMP -ing from this mixed (predominantly triplet) state allows access to high vibrational levels of CO (X(1)Σ(+)). The success of the approach, which avoids the use of vacuum UV radiation in any of the excitation steps, is proven by laser induced fluorescence and resonance enhanced multi-photon ionization spectroscopy.

Production of a beam of highly vibrationally excited CO using perturbations

NASA Astrophysics Data System (ADS)

Bartels, Nils; Schäfer, Tim; Hühnert, Jens; Field, Robert W.; Wodtke, Alec M.

2012-06-01

An intense molecular beam of CO (X1Σ+) in high vibrational states (v = 17, 18) was produced by a new approach that we call PUMP - PUMP - PERTURB and DUMP. The basic idea is to access high vibrational states of CO e3Σ- via a two-photon doubly resonant transition that is perturbed by the A1Π state. DUMP -ing from this mixed (predominantly triplet) state allows access to high vibrational levels of CO (X1Σ+). The success of the approach, which avoids the use of vacuum UV radiation in any of the excitation steps, is proven by laser induced fluorescence and resonance enhanced multi-photon ionization spectroscopy.

Detection limits of organic compounds achievable with intense, short-pulse lasers.

PubMed

Miles, Jordan; De Camillis, Simone; Alexander, Grace; Hamilton, Kathryn; Kelly, Thomas J; Costello, John T; Zepf, Matthew; Williams, Ian D; Greenwood, Jason B

2015-06-21

Many organic molecules have strong absorption bands which can be accessed by ultraviolet short pulse lasers to produce efficient ionization. This resonant multiphoton ionization scheme has already been exploited as an ionization source in time-of-flight mass spectrometers used for environmental trace analysis. In the present work we quantify the ultimate potential of this technique by measuring absolute ion yields produced from the interaction of 267 nm femtosecond laser pulses with the organic molecules indole and toluene, and gases Xe, N2 and O2. Using multiphoton ionization cross sections extracted from these results, we show that the laser pulse parameters required for real-time detection of aromatic molecules at concentrations of one part per trillion in air and a limit of detection of a few attomoles are achievable with presently available commercial laser systems. The potential applications for the analysis of human breath, blood and tissue samples are discussed.

Laser-induced breakup of helium 3S 1s2s with intermediate doubly excited states

NASA Astrophysics Data System (ADS)

Simonsen, A. S.; Bachau, H.; Førre, M.

2014-02-01

Solving the time-dependent Schrödinger equation in full dimensionality for two electrons, it is found that in the XUV regime the two-photon double ionization dynamics of He(1s2s) is predominantly dictated by the process of resonance enhanced multiphoton ionization via doubly excited states (DESs). We have studied a pump-probe scenario where the full laser-driven breakup of the 3S 1s2s metastable state is dominated by intermediate quasiresonant excitation to doubly excited (autoionizing) states in the 3Po series. Clear evidence of multipath interference effects is revealed in the resulting angular distributions of the ejected electrons in cases where more than one intermediate DES is populated in the process.

Total angular momenta of high-lying odd levels of U I at ∼ 4 eV using resonance ionization laser polarization spectroscopy

NASA Astrophysics Data System (ADS)

Rath, Asawari D.; Kundu, S.; Ray, A. K.

2018-02-01

Laser induced photoionization of atoms shows significant dependence on the choice of polarizations of lasers. In multi-step, multi-photon excitation and subsequent ionization of atoms different polarization combinations of the exciting lasers lead to distinctly different ion yields. This fact is exploited in this work to determine total angular momenta of odd-parity energy levels of U I lying at ∼ 4 eV from its ground level using resonance ionization laser polarization spectroscopy in time of flight mass spectrometer. These levels are populated by two-step resonant excitation using two pulsed dye lasers with preset polarizations of choice followed by nonresonant ionization by third laser. The dependence of ionization yield on specific polarizations of the first two lasers is studied experimentally for each level under consideration. This dependence when compared to simulations makes possible unambiguous assignment of J angular momenta to these levels.

Ion-Pair States in Triplet Molecular Hydrogen

NASA Astrophysics Data System (ADS)

Setzer, W.; Baker, B. C.; Ashman, S.; Morgan, T. J.

2016-05-01

An experimental search is underway to observe the long range triplet ionic states H+ H- of molecular hydrogen. Resonantly enhanced multi-photon ionization of the metastable c 3∏u- 2 pπ state is used access to the R(1)nd1 n = 21 Rydberg state that serves as an intermediate stepping stone state to probe the energy region above the ionization limit with a second tunable laser photon. The metastable state is prepared by electron capture of 6 keV H2+ions in potassium in a molecular beam. Formation of the H+ H- triplet configuration involves triplet excited states of the H- ion, especially the 2p23Pe state, the second bound state of H- predicted to exist with a lifetime long compared to typical auto ionization lifetimes but not yet observed experimentally. Details of the experiment and preliminary results to date will be presented at the conference.

An alternative mechanism for spin-forbidden photo-ionization of diatomic molecules and its rotation-electronic selection rules

NASA Astrophysics Data System (ADS)

Chiu, Ying-Nan; Chiu, Lue-Yung Chow

1990-02-01

The spin-forbidden photo-ionization of diatomic molecules is proposed. Spin orbit interaction is invoked, resulting in the correction and mixing of the wave functions of different multiplicities. The rotation-electronic selection rules given by Dixit and McKoy (1986) for Hund's case a based on the conventional mechanism of electric dipole transition are rederived and expressed in a different format. This new format permits the generalization of the selection rules to other photoionization transitions caused by the magnetic dipole, the electric quadrupole, and the two- and three-photon operators. These selection rules, which are for transitions from one specific rotational level of a given Kronig reflection symmetry to another, will help understand rotational branching and the dynamics of interaction in the excited state. They will also help in the selective preparation of well-defined rovibronic states in resonant-enhanced multi-photon ionization processes.

Ionization-induced solvent migration in acetanilide-methanol clusters inferred from isomer-selective infrared spectroscopy.

PubMed

Weiler, Martin; Nakamura, Takashi; Sekiya, Hiroshi; Dopfer, Otto; Miyazaki, Mitsuhiko; Fujii, Masaaki

2012-12-07

We present the resonance-enhanced multiphoton ionization, infrared-ultraviolet hole burning (IR-UV HB), and IR dip spectra of the trans-acetanilide-methanol (AA-MeOH) cluster in the S(0), S(1), and cationic ground state (D(0)) in a supersonic jet. The IR-UV HB spectra demonstrate the co-existence of two isomers in S(0,1), in which MeOH binds either to the NH or the CO site of the peptide linkage in AA, denoted as AA(NH)-MeOH and AA(CO)-MeOH. When AA(CO)-MeOH is selectively ionized, its IR spectrum in D(0) is the same as that measured for AA(+) (NH)-MeOH. Thus, photoionization of AA(CO)-MeOH induces migration of MeOH from the CO to the NH site with 100% yield. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Roles of Tunneling, Multiphoton Ionization, and Cascade Ionization for Femtosecond Optical Breakdown in Aqueous Media

DTIC Science & Technology

2009-09-01

observed in the wavelength dependence of femtosecond breakdown would indicate a significant role of multiphoton ionization compared to tunneling ...relevant for femtosecond breakdown, and tunnel ionization featuring no Ith() dependence becomes ever more with decreasing pulse duration. However, it...c) Figure 4.22 Wavelength dependence of ionization probabilities by a) avalanche, b) multiphoton, and c) tunneling ionization. 1

Ultrafast photodissociation dynamics of 1,4-diiodobenzene

NASA Astrophysics Data System (ADS)

Stankus, Brian; Zotev, Nikola; Rogers, David M.; Gao, Yan; Odate, Asami; Kirrander, Adam; Weber, Peter M.

2018-05-01

The photodissociation dynamics of 1,4-diiodobenzene is investigated using ultrafast time-resolved photoelectron spectroscopy. Following excitation by laser pulses at 271 nm, the excited-state dynamics is probed by resonance-enhanced multiphoton ionization with 405 nm probe pulses. A progression of Rydberg states, which come into resonance sequentially, provide a fingerprint of the dissociation dynamics of the molecule. The initial excitation decays with a lifetime of 33 ± 4 fs, in good agreement with a previous study. The spectrum is interpreted by reference to ab initio calculations at the CASPT2(18,14) level, including spin-orbit coupling. We propose that both the 5B1 and 6B1 states are excited initially, and based on the calculations, we identify diabatic spin-orbit coupled states corresponding to the main dissociation pathways.

Rotational spectroscopy with an optical centrifuge.

PubMed

Korobenko, Aleksey; Milner, Alexander A; Hepburn, John W; Milner, Valery

2014-03-07

We demonstrate a new spectroscopic method for studying electronic transitions in molecules with extremely broad range of angular momentum. We employ an optical centrifuge to create narrow rotational wave packets in the ground electronic state of (16)O2. Using the technique of resonance-enhanced multi-photon ionization, we record the spectrum of multiple ro-vibrational transitions between X(3)Σg(-) and C(3)Πg electronic manifolds of oxygen. Direct control of rotational excitation, extending to rotational quantum numbers as high as N ≳ 120, enables us to interpret the complex structure of rotational spectra of C(3)Πg beyond thermally accessible levels.

A method of extracting speed-dependent vector correlations from 2 + 1 REMPI ion images.

PubMed

Wei, Wei; Wallace, Colin J; Grubb, Michael P; North, Simon W

2017-07-07

We present analytical expressions for extracting Dixon's bipolar moments in the semi-classical limit from experimental anisotropy parameters of sliced or reconstructed non-sliced images. The current method focuses on images generated by 2 + 1 REMPI (Resonance Enhanced Multi-photon Ionization) and is a necessary extension of our previously published 1 + 1 REMPI equations. Two approaches for applying the new equations, direct inversion and forward convolution, are presented. As demonstration of the new method, bipolar moments were extracted from images of carbonyl sulfide (OCS) photodissociation at 230 nm and NO 2 photodissociation at 355 nm, and the results are consistent with previous publications.

Mechanisms of H{sub 2}O desorption from amorphous solid water by 157-nm irradiation: An experimental and theoretical study

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

DeSimone, Alice J.; Crowell, Vernon D.; Sherrill, C. David

2013-10-28

The photodesorption of water molecules from amorphous solid water (ASW) by 157-nm irradiation has been examined using resonance-enhanced multiphoton ionization. The rotational temperature has been determined, by comparison with simulations, to be 425 ± 75 K. The time-of-flight spectrum of H{sub 2}O (v= 0) has been fit with a Maxwell-Boltzmann distribution with a translational temperature of 700 ± 200 K (0.12 ± 0.03 eV). H{sup +} and OH{sup +} fragment ions have been detected with non-resonant multiphoton ionization, indicating vibrationally excited parent water molecules with translational energies of 0.24 ± 0.08 eV. The cross section for water removal from ASWmore » by 7.9-eV photons near 100 K is (6.9 ± 1.8) × 10{sup −20} cm{sup 2} for >10 L H{sub 2}O exposure. Electronic structure computations have also probed the excited states of water and the mechanisms of desorption. Calculated electron attachment and detachment densities show that exciton delocalization leads to a dipole reversal state in the first singlet excited state of a model system of hexagonal water ice. Ab Initio Molecular Dynamics simulations show possible desorption of a photo-excited water molecule from this cluster, though the non-hydrogen bonded OH bond is stretched significantly before desorption. Potential energy curves of this OH stretch in the electronic excited state show a barrier to dissociation, lending credence to the dipole reversal mechanism.« less

Optimized cell geometry for buffer-gas-cooled molecular-beam sources

NASA Astrophysics Data System (ADS)

Singh, Vijay; Samanta, Amit K.; Roth, Nils; Gusa, Daniel; Ossenbrüggen, Tim; Rubinsky, Igor; Horke, Daniel A.; Küpper, Jochen

2018-03-01

We have designed, constructed, and commissioned a cryogenic helium buffer-gas source for producing a cryogenically cooled molecular beam and evaluated the effect of different cell geometries on the intensity of the produced molecular beam, using ammonia as a test molecule. Planar and conical entrance and exit geometries are tested. We observe a threefold enhancement in the NH3 signal for a cell with planar entrance and conical-exit geometry, compared to that for a typically used "boxlike" geometry with planar entrance and exit. These observations are rationalized by flow field simulations for the different buffer-gas cell geometries. The full thermalization of molecules with the helium buffer gas is confirmed through rotationally resolved resonance-enhanced multiphoton ionization spectra yielding a rotational temperature of 5 K.

Interatomic Coulombic decay cascades in multiply excited neon clusters

PubMed Central

Nagaya, K.; Iablonskyi, D.; Golubev, N. V.; Matsunami, K.; Fukuzawa, H.; Motomura, K.; Nishiyama, T.; Sakai, T.; Tachibana, T.; Mondal, S.; Wada, S.; Prince, K. C.; Callegari, C.; Miron, C.; Saito, N.; Yabashi, M.; Demekhin, Ph. V.; Cederbaum, L. S.; Kuleff, A. I.; Yao, M.; Ueda, K.

2016-01-01

In high-intensity laser light, matter can be ionized by direct multiphoton absorption even at photon energies below the ionization threshold. However on tuning the laser to the lowest resonant transition, the system becomes multiply excited, and more efficient, indirect ionization pathways become operative. These mechanisms are known as interatomic Coulombic decay (ICD), where one of the species de-excites to its ground state, transferring its energy to ionize another excited species. Here we show that on tuning to a higher resonant transition, a previously unknown type of interatomic Coulombic decay, intra-Rydberg ICD occurs. In it, de-excitation of an atom to a close-lying Rydberg state leads to electron emission from another neighbouring Rydberg atom. Moreover, systems multiply excited to higher Rydberg states will decay by a cascade of such processes, producing even more ions. The intra-Rydberg ICD and cascades are expected to be ubiquitous in weakly-bound systems exposed to high-intensity resonant radiation. PMID:27917867

Surface Temperature Dependence of Hydrogen Ortho-Para Conversion on Amorphous Solid Water.

PubMed

Ueta, Hirokazu; Watanabe, Naoki; Hama, Tetsuya; Kouchi, Akira

2016-06-24

The surface temperature dependence of the ortho-to-para conversion of H_{2} on amorphous solid water is first reported. A combination of photostimulated desorption and resonance-enhanced multiphoton ionization techniques allowed us to sensitively probe the conversion on the surface of amorphous solid water at temperatures of 9.2-16 K. Within a narrow temperature window of 8 K, the conversion time steeply varied from ∼4.1×10^{3} to ∼6.4×10^{2}  s. The observed temperature dependence is discussed in the context of previously suggested models and the energy dissipation process. The two-phonon process most likely dominates the conversion rate at low temperatures.

Detailed Observation of Multiphoton Emission Enhancement from a Single Colloidal Quantum Dot Using a Silver-Coated AFM Tip.

PubMed

Takata, Hiroki; Naiki, Hiroyuki; Wang, Li; Fujiwara, Hideki; Sasaki, Keiji; Tamai, Naoto; Masuo, Sadahiro

2016-09-14

The enhancement of multiphoton emission from a single colloidal nanocrystal quantum dot (NQD) interacting with a plasmonic nanostructure was investigated using a silver-coated atomic force microscopy tip (AgTip) as the plasmonic nanostructure. Using the AgTip, which exhibited a well-defined localized surface plasmon (LSP) resonance band, we controlled the spectral overlap and the distance between the single NQD and the AgTip. The emission behavior of the single NQD when approaching the AgTip at the nanometer scale was measured using off-resonance (405 nm) and resonance (465 nm) excitation of the LSP. We directly observed the conversion of the single-photon emission from a single NQD to multiphoton emission with reduction of the emission lifetime at both excitation wavelengths as the NQD-AgTip distance decreased, whereas a decrease and increase in the emission intensity were observed at 405 and 465 nm excitation, respectively. By combining theoretical analysis and the numerical simulation of the AgTip, we deduced that the enhancement of the multiphoton emission was caused by the quenching of the single-exciton state due to the energy transfer from the NQD to the AgTip and that the emission intensity was increased by enhancement of the excitation rate due to the electric field of the LSP on the AgTip. These results provide evidence that the photon statistics and the photon flux from the single NQD can be manipulated by the plasmonic nanostructure through control of the spectral overlap and the distance.

Spectroscopic Constants of the Known Electronic States of Lead Monofluoride

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

McRaven, C.P.; Sivakumar, P.; Shafer-Ray, N.E.

2010-08-01

Based on measurements made by mass-resolved 1 + 1{prime} + 1{double_prime} resonance-enhanced multiphoton ionization spectroscopy, we have determined new molecular constants describing the rotational and fine structure levels of the B, D, E, and F states of the most abundant isotopic variant {sup 208}Pb{sup 19}F, and we summarize the spectroscopic constants for all the know electronic states of the radical. Many spectroscopic constants for the isotopologues {sup 206}Pb{sup 19}F and {sup 207}Pb{sup 19}F have also been determined. The symmetry of the D-state is found to be {sup 2}{pi}{sub 1/2}, and the F-state is found to be an {Omega} = 3/2more » state.« less

SFC-APLI-(TOF)MS: Hyphenation of Supercritical Fluid Chromatography to Atmospheric Pressure Laser Ionization Mass Spectrometry.

PubMed

Klink, Dennis; Schmitz, Oliver Johannes

2016-01-05

Atmospheric-pressure laser ionization mass spectrometry (APLI-MS) is a powerful method for the analysis of polycyclic aromatic hydrocarbon (PAH) molecules, which are ionized in a selective and highly sensitive way via resonance-enhanced multiphoton ionization. APLI was presented in 2005 and has been hyphenated successfully to chromatographic separation techniques like high performance liquid chromatography (HPLC) and gas chromatography (GC). In order to expand the portfolio of chromatographic couplings to APLI, a new hyphenation setup of APLI and supercritical-fluid chromatography (SFC) was constructed and aim of this work. Here, we demonstrate the first hyphenation of SFC and APLI in a simple designed way with respect to different optimization steps to ensure a sensitive analysis. The new setup permits qualitative and quantitative determination of native and also more polar PAH molecules. As a result of the altered ambient characteristics within the source enclosure, the quantification of 1-hydroxypyrene (1-HP) in human urine is possible without prior derivatization. The limit of detection for 1-HP by SFC-APLI-TOF(MS) was found to be 0.5 μg L(-1), which is lower than the 1-HP concentrations found in exposed persons.

Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection.

PubMed

Lehmann, C Stefan; Ram, N Bhargava; Powis, Ivan; Janssen, Maurice H M

2013-12-21

Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations. Qualitative agreement is observed between the experimental results and the theoretical calculations of the Legendre moments representing the angular distribution for the two enantiomers. The electron-ion coincidence technique using multiphoton ionization opens new directions in table-top analytical mass-spectrometric applications of mixtures of chiral molecules.

Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection

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

Lehmann, C. Stefan; Ram, N. Bhargava; Janssen, Maurice H. M., E-mail: m.h.m.janssen@vu.nl

2013-12-21

Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flightmore » mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations. Qualitative agreement is observed between the experimental results and the theoretical calculations of the Legendre moments representing the angular distribution for the two enantiomers. The electron-ion coincidence technique using multiphoton ionization opens new directions in table-top analytical mass-spectrometric applications of mixtures of chiral molecules.« less

Dissociation of heme from gaseous myoglobin ions studied by infrared multiphoton dissociation spectroscopy and Fourier-transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Wang, Yi-Sheng; Sabu, Sahadevan; Wei, Shih-Chia; Josh Kao, C.-M.; Kong, Xianglei; Liau, Shing-Chih; Han, Chau-Chung; Chang, Huan-Cheng; Tu, Shih-Yu; Kung, A. H.; Zhang, John Z. H.

2006-10-01

Detachment of heme prosthetic groups from gaseous myoglobin ions has been studied by collision-induced dissociation and infrared multiphoton dissociation in combination with Fourier-transform ion cyclotron resonance mass spectrometry. Multiply charged holomyoglobin ions (hMbn +) were generated by electrospray ionization and transferred to an ion cyclotron resonance cell, where the ions of interest were isolated and fragmented by either collision with Ar atoms or irradiation with 3μm photons, producing apomyoglobin ions (aMbn +). Both charged heme loss (with [Fe(III)-heme]+ and aMb(n-1)+ as the products) and neutral heme loss (with [Fe(II)-heme] and aMbn + as the products) were detected concurrently for hMbn + produced from a myoglobin solution pretreated with reducing reagents. By reference to Ea=0.9eV determined by blackbody infrared radiative dissociation for charged heme loss of ferric hMbn +, an activation energy of 1.1eV was deduced for neutral heme loss of ferrous hMbn + with n =9 and 10.

New diagnostic methods for laser plasma- and microwave-enhanced combustion

PubMed Central

Miles, Richard B; Michael, James B; Limbach, Christopher M; McGuire, Sean D; Chng, Tat Loon; Edwards, Matthew R; DeLuca, Nicholas J; Shneider, Mikhail N; Dogariu, Arthur

2015-01-01

The study of pulsed laser- and microwave-induced plasma interactions with atmospheric and higher pressure combusting gases requires rapid diagnostic methods that are capable of determining the mechanisms by which these interactions are taking place. New rapid diagnostics are presented here extending the capabilities of Rayleigh and Thomson scattering and resonance-enhanced multi-photon ionization (REMPI) detection and introducing femtosecond laser-induced velocity and temperature profile imaging. Spectrally filtered Rayleigh scattering provides a method for the planar imaging of temperature fields for constant pressure interactions and line imaging of velocity, temperature and density profiles. Depolarization of Rayleigh scattering provides a measure of the dissociation fraction, and multi-wavelength line imaging enables the separation of Thomson scattering from Rayleigh scattering. Radar REMPI takes advantage of high-frequency microwave scattering from the region of laser-selected species ionization to extend REMPI to atmospheric pressures and implement it as a stand-off detection method for atomic and molecular species in combusting environments. Femtosecond laser electronic excitation tagging (FLEET) generates highly excited molecular species and dissociation through the focal zone of the laser. The prompt fluorescence from excited molecular species yields temperature profiles, and the delayed fluorescence from recombining atomic fragments yields velocity profiles. PMID:26170432

Conformational analysis of quinine and its pseudo enantiomer quinidine: a combined jet-cooled spectroscopy and vibrational circular dichroism study.

PubMed

Sen, Ananya; Bouchet, Aude; Lepère, Valeria; Le Barbu-Debus, Katia; Scuderi, D; Piuzzi, F; Zehnacker-Rentien, A

2012-08-16

Laser-desorbed quinine and quinidine have been studied in the gas phase by combining supersonic expansion with laser spectroscopy, namely, laser-induced fluorescence (LIF), resonance-enhanced multiphoton ionization (REMPI), and IR-UV double resonance experiments. Density funtional theory (DFT) calculations have been done in conjunction with the experimental work. The first electronic transition of quinine and quinidine is of π-π* nature, and the studied molecules weakly fluoresce in the gas phase, in contrast to what was observed in solution (Qin, W. W.; et al. J. Phys. Chem. C2009, 113, 11790). The two pseudo enantiomers quinine and quinidine show limited differences in the gas phase; their main conformation is of open type as it is in solution. However, vibrational circular dichroism (VCD) experiments in solution show that additional conformers exist in condensed phase for quinidine, which are not observed for quinine. This difference in behavior between the two pseudo enantiomers is discussed.

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

Avetissian, H. K.; Avchyan, B. R.; Mkrtchian, G. F.

The multiphoton resonant excitation of three-level atoms by the two laser fields of different frequencies is investigated. The time evolution of the system and analytical solutions expressing Rabi oscillations of the probability amplitudes at the two-color multiphoton resonant excitation are found using a nonperturbative resonant approach. The specific examples for experimental implementation of two-color multiphoton resonant excitation of hydrogen atoms are considered.

In situ optical measurements for characterization of flame species and remote sensing

NASA Astrophysics Data System (ADS)

Cullum, Brian Michael

1998-12-01

The following dissertation describes the use of spectroscopic techniques for both characterization of combustion intermediates and remote chemical sensing. The primary techniques that have been used for these measurements include, laser-induced fluorescence (LIF), time resolved LIF, resonance enhanced multiphoton ionization (REMPI) and Raman spectroscopy. A simple and quantitative means of measuring the efficiency of halogenated flame retardants is described, using laser-induced fluorescence (LIF). Intensity based LIF measurements of OH radical have been used to quantitatively measure the efficacy of halogenated flame retardant/polymer plaques. Temporally resolved LIF has been used to determine the extent to which the chemical kinetic theory of flame retardation applies to the effect of these compounds on combustion. We have shown that LIF of OH radicals is a very sensitive means of measuring the efficiency of these flame retardants as well as the giving information about the nature of flame retardation. In addition, we have developed a technique for the introduction of insoluble polymer plaques into a flame for fluorescence analysis. A high power pulsed Nd:YAG laser is used to ablate the sample into the flame while a second pulse from a dye laser is used to measure the LIF of OH radicals. Spectroscopic techniques are also very useful for trace remote analysis of environmental pollutants via optical fibers. A simple fiber-optic probe suitable for remote analysis using resonance enhanced multiphoton ionization (REMPI) has been developed for this purpose and is used to determine the toluene/gasoline concentration in water samples via a headspace measurement. The limit of detection for toluene in water using this probe is 0.54 ppb (wt/wt) with a sample standard deviation of 0.02 ppb (wt/wt). Another technique that has great potential for optical sensing is fluorescence lifetime imaging. A new method for measuring fluorescence lifetime images of quickly decaying species has been developed. This method employs a high powered pulsed laser that excites the fluorescent species in a dual pulse manner, and a non-gated charge coupled device (CCD) for detection of the fluorescence. Unlike other fluorescence lifetime imaging methods, this technique has the potential of monitoring fluorescent species with picosecond lifetimes.

Field enhancement of multiphoton induced luminescence processes in ZnO nanorods

NASA Astrophysics Data System (ADS)

Hyyti, Janne; Perestjuk, Marko; Mahler, Felix; Grunwald, Rüdiger; Güell, Frank; Gray, Ciarán; McGlynn, Enda; Steinmeyer, Günter

2018-03-01

The near-ultraviolet photoluminescence of ZnO nanorods induced by multiphoton absorption of unamplified Ti:sapphire pulses is investigated. Power dependence measurements have been conducted with an adaptation of the ultrashort pulse characterization method of interferometric frequency-resolved optical gating. These measurements enable the separation of second harmonic and photoluminescence bands due to their distinct coherence properties. A detailed analysis yields fractional power dependence exponents in the range of 3-4, indicating the presence of multiple nonlinear processes. The range in measured exponents is attributed to differences in local field enhancement, which is supported by independent photoluminescence and structural measurements. Simulations based on Keldysh theory suggest contributions by three- and four-photon absorption as well as avalanche ionization in agreement with experimental findings.

Determination of polycyclic aromatic hydrocarbons and their nitro-, amino-derivatives absorbed on particulate matter 2.5 by multiphoton ionization mass spectrometry using far-, deep-, and near-ultraviolet femtosecond lasers.

PubMed

Tang, Yuanyuan; Imasaka, Tomoko; Yamamoto, Shigekazu; Imasaka, Totaro

2016-06-01

Multiphoton ionization processes of parent-polycyclic aromatic hydrocarbons (PPAHs), nitro-PAHs (NPAHs), and amino-PAHs (APAHs) were examined by gas chromatography combined with time-of-flight mass spectrometry using a femtosecond Ti:sapphire laser as the ionization source. The efficiency of multiphoton ionization was examined using lasers emitting in the far-ultraviolet (200 nm), deep-ultraviolet (267 nm), and near-ultraviolet (345 nm) regions. The largest signal intensities were obtained when the far-ultraviolet laser was employed. This favorable result can be attributed to the fact that these compounds have the largest molar absorptivities in the far-ultraviolet region. On the other hand, APAHs were ionized more efficiently than NPAHs in the near-ultraviolet region because of their low ionization energies. A sample extracted from a real particulate matter 2.5 (PM2.5) sample was measured, and numerous signal peaks arising from PAH and its analogs were observed at 200 nm. On the other hand, only a limited number of signed peaks were observed at 345 nm, some of which were signed to PPAHs, NPAHs, and APAHs. Thus, multiphoton ionization mass spectrometry has potential for the use in comprehensive analysis of toxic environmental pollutants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Torsional, Vibrational and Vibration-Torsional Levels in the S_{1} and Ground Cationic D_{0}^{+} States of Para-Fluorotoluene

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Tuttle, William Duncan; Whalley, Laura E.; Claydon, Andrew; Carter, Joseph H.; Wright, Timothy G.

2017-06-01

The S_{1} electronic state and ground state of the cation of para-fluorotoluene (pFT) have been investigated using resonance-enhanced multiphoton ionization (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy. Here we focus on the low wavenumber region where a number of "pure" torsional, fundamental vibrational and vibration-torsional levels are expected; assignments of observed transitions are discussed, which are compared to results of published work on toluene (methylbenzene) from the Lawrance group. The similarity in the activity observed in the excitation spectrum of the two molecules is striking. A. M. Gardner, W. D. Tuttle, L. Whalley, A. Claydon, J. H. Carter and T. G. Wright, J. Chem. Phys., 145, 124307 (2016). J. R. Gascooke, E. A. Virgo, and W. D. Lawrance J. Chem. Phys., 143, 044313 (2015).

Multi-Wavelength Laser Transmitter for the Two-Step Laser Time-of-Flight Mass Spectrometer

NASA Technical Reports Server (NTRS)

Yu, Anthony W.; Li, Steven X.; Fahey, Molly E.; Grubisic, Andrej; Farcy, Benjamin J.; Uckert, Kyle; Li, Xiang; Getty, Stephanie

2017-01-01

Missions to diverse Outer Solar System bodies will require investigations that can detect a wide range of organics in complex mixtures, determine the structure of selected molecules, and provide powerful insights into their origin and evolution. Previous studies from remote spectroscopy of the Outer Solar System showed a diverse population of macromolecular species that are likely to include aromatic and conjugated hydrocarbons with varying degrees of methylation and nitrile incorporation. In situ exploration of Titan's upper atmosphere via mass and plasma spectrometry has revealed a complex mixture of organics. Similar material is expected on the Ice Giants, their moons, and other Outer Solar System bodies, where it may subsequently be deposited onto surface ices. It is evident that the detection of organics on other planetary surfaces provides insight into the chemical and geological evolution of a Solar System body of interest and can inform our understanding of its potential habitability. We have developed a prototype two-step laser desorption/ionization time-of-flight mass spectrometer (L2MS) instrument by exploiting the resonance-enhanced desorption of analyte. We have successfully demonstrated the ability of the L2MS to detect hydrocarbons in organically-doped analog minerals, including cryogenic Ocean World-relevant ices and mixtures. The L2MS instrument operates by generating a neutral plume of desorbed analyte with an IR desorption laser pulse, followed at a delay by a ultraviolet (UV) laser pulse, ionizing the plume. Desorption of the analyte, including trace organic species, may be enhanced by selecting the wavelength of the IR desorption laser to coincide with IR absorption features associated with vibration transitions of minerals or organic functional groups. In this effort, a preliminary laser developed for the instrument uses a breadboard mid-infrared (MIR) desorption laser operating at a discrete 3.475 µm wavelength, and a breadboard UV ionization laser operating at a wavelength of 266 nm. The MIR wavelength was selected to overlap the C-H stretch vibrational transition of certain aromatic hydrocarbons, and the UV wavelength provides additional selectivity to aromatic species via UV resonance-enhanced multiphoton ionization effects. The use of distinct laser wavelengths allows efficient coupling to the vibrational and electronic spectra of the analyte in independent desorption and ionization steps, mitigating excess energy that can lead to fragmentation during the ionization process and leading to selectivity that can aid in data interpretation.

Computational code in atomic and nuclear quantum optics: Advanced computing multiphoton resonance parameters for atoms in a strong laser field

NASA Astrophysics Data System (ADS)

Glushkov, A. V.; Gurskaya, M. Yu; Ignatenko, A. V.; Smirnov, A. V.; Serga, I. N.; Svinarenko, A. A.; Ternovsky, E. V.

2017-10-01

The consistent relativistic energy approach to the finite Fermi-systems (atoms and nuclei) in a strong realistic laser field is presented and applied to computing the multiphoton resonances parameters in some atoms and nuclei. The approach is based on the Gell-Mann and Low S-matrix formalism, multiphoton resonance lines moments technique and advanced Ivanov-Ivanova algorithm of calculating the Green’s function of the Dirac equation. The data for multiphoton resonance width and shift for the Cs atom and the 57Fe nucleus in dependence upon the laser intensity are listed.

Multiphoton Rydberg and valence dynamics of CH3Br probed by mass spectrometry and slice imaging.

PubMed

Hafliðason, Arnar; Glodic, Pavle; Koumarianou, Greta; Samartzis, Peter C; Kvaran, Ágúst

2018-06-18

The multiphoton dynamics of CH3Br were probed by Mass Resolved MultiPhoton Ionization (MR-MPI), Slice Imaging and Photoelectron Imaging in the two-photon excitation region of 66 000 to 80 000 cm-1. Slice images of the CH3+ and Br+ photoproducts of ten two-photon resonant transitions to np and nd Rydberg states of the parent molecule were recorded. CH3+ ions dominate the mass spectra. Kinetic energy release spectra (KERs) were derived from slice and photoelectron images and anisotropy parameters were extracted from the angular distributions of the ions to identify the processes and the dynamics involved. At all wavelengths we observe three-photon excitations, via the two-photon resonant transitions to molecular Rydberg states, forming metastable, superexcited (CH3Br#) states which dissociate to form CH3 Rydberg states (CH3**) along with Br/Br*. A correlation between the parent Rydberg states excited and CH3** formed is evident. For the three highest excitation energies used, the CH3Br# metastable states also generate high kinetic energy fragments of CH3(X) and Br/Br*. In addition for two out of these three wavelengths we also measure one-photon photolysis of CH3Br in the A band forming CH3(X) in various vibrational modes and bromine atoms in the ground (Br) and spin-orbit excited (Br*) states.

Effects of the Carrier-Envelope Phase in the Multiphoton Ionization Regime

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

Nakajima, Takashi; Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581; Watanabe, Shuntaro

2006-06-02

We theoretically investigate the effects of the carrier-envelope phase of few-cycle laser pulses in the multiphoton ionization regime. For atoms with low ionization potential, total ionization yield barely exhibits phase dependence, as expected. However, population of some bound states clearly shows phase dependence. This implies that the measurement of the carrier-envelope phase would be possible through the photoemission between bound states without energy-and-angle-resolved photoelectron detection. The considered scheme could be particularly useful to measure the carrier-envelope phase for a light source without an amplifier, such as a laser oscillator, which cannot provide sufficient pulse energy to induce tunneling ionization.

The generation of a tunable laser emission in the vacuum ultraviolet and its application to supersonic jet/multiphoton ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Uchimura, Tomohiro; Onoda, Takayuki; Lin, Cheng-Huang; Imasaka, Totaro

1999-08-01

An optical parametric oscillator and a Ti:sapphire laser are used as a pump source for the generation of high-order vibrational stimulated Raman emission in the vacuum ultraviolet region. This tunable laser is employed as an excitation/ionization source in a supersonic jet/multiphoton ionization/time-of-flight mass spectrometric study of benzene. The merits and potential advantages of this approach are discussed in this study.

Resonantly enhanced multiple exciton generation through below-band-gap multi-photon absorption in perovskite nanocrystals.

PubMed

Manzi, Aurora; Tong, Yu; Feucht, Julius; Yao, En-Ping; Polavarapu, Lakshminarayana; Urban, Alexander S; Feldmann, Jochen

2018-04-17

Multi-photon absorption and multiple exciton generation represent two separate strategies for enhancing the conversion efficiency of light into usable electric power. Targeting below-band-gap and above-band-gap energies, respectively, to date these processes have only been demonstrated independently. Here we report the combined interaction of both nonlinear processes in CsPbBr 3 perovskite nanocrystals. We demonstrate nonlinear absorption over a wide range of below-band-gap excitation energies (0.5-0.8 E g ). Interestingly, we discover high-order absorption processes, deviating from the typical two-photon absorption, at specific energetic positions. These energies are associated with a strong enhancement of the photoluminescence intensity by up to 10 5 . The analysis of the corresponding energy levels reveals that the observed phenomena can be ascribed to the resonant creation of multiple excitons via the absorption of multiple below-band-gap photons. This effect may open new pathways for the efficient conversion of optical energy, potentially also in other semiconducting materials.

Measurements of the Activation Energies for Atomic Hydrogen Diffusion on Pure Solid CO

NASA Astrophysics Data System (ADS)

Kimura, Y.; Tsuge, M.; Pirronello, V.; Kouchi, A.; Watanabe, N.

2018-05-01

The diffusion of hydrogen atoms on dust grains is a key process in the formation of interstellar H2 and some hydrogenated molecules such as formaldehyde and methanol. We investigate the adsorption and diffusion of H atoms on pure solid CO as an analog of dust surfaces observed toward some cold interstellar regions. Using a combination of photostimulated desorption and resonance-enhanced multiphoton ionization methods to detect H atoms directly, the relative adsorption probabilities and diffusion coefficients of the H atoms are measured on pure solid CO at 8, 12, and 15 K. There is little difference between the diffusion coefficients of the hydrogen and deuterium atoms, indicating that the diffusion is limited by thermal hopping. The activation energies controlling the H-atom diffusion depend on the surface temperature, and values of 22, 30, and ∼37 meV were obtained for 8, 12, and 15 K, respectively.

Spectroscopic study on deuterated benzenes. II. High-resolution laser spectroscopy and rotational structure in the S{sub 1} state

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

Kunishige, Sachi; Katori, Toshiharu; Baba, Masaaki, E-mail: baba@kuchem.kyoto-u.ac.jp

High-resolution spectra of the S{sub 1}←S{sub 0} transition in jet-cooled deuterated benzenes were observed using pulse dye amplification of single-mode laser light and mass-selective resonance enhanced multiphoton ionization (REMPI) detection. The vibrational and rotational structures were accurately analyzed for the vibronic levels in the S{sub 1} state. The degenerate 6{sup 1} levels of C{sub 6}H{sub 6} or C{sub 6}D{sub 6} are split into 6a{sup 1} and 6b{sup 1} in many of deuterated benzenes. The rigid-rotor rotational constants were assessed and found to be slightly different between 6a and 6b because of different mean molecular structures. Their rotational levels are significantlymore » shifted by Coriolis interactions. It was found that the Coriolis parameter proportionally changed with the number of substituted D atoms.« less

Torsional, Vibrational and Vibration-Torsional Levels in the S_{1} and Ground Cationic D_{0}^{+} States of Para-Xylene

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Tuttle, William Duncan; Groner, Peter; Wright, Timothy G.

2017-06-01

Insight gained from examining the "pure" torsional, vibrational and vibration-torsional (vibtor) levels of the single rotor molecules: toluene (methylbenzene) and para-fluorotoluene (pFT), is applied to the double rotor para-xylene (p-dimethylbenzene) molecule . Resonance-enhanced multiphoton ionization (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy are employed in order to investigate the S_{1} and ground cationic states of para-xylene. Observed transitions are assigned in the full molecular symmetry group (G_{72}) for the first time. J. R. Gascooke, E. A. Virgo, and W. D. Lawrance, J. Chem. Phys., 143, 044313 (2015). A. M. Gardner, W. D. Tuttle, L. Whalley, A. Claydon, J. H. Carter and T. G. Wright, J. Chem. Phys., 145, 124307 (2016). A. M. Gardner, W. D. Tuttle, P. Groner and T. G. Wright, J. Chem. Phys., (2017, in press).

Mass-Selective Chiral Analysis

NASA Astrophysics Data System (ADS)

Boesl, Ulrich; Kartouzian, Aras

2016-06-01

Three ways of realizing mass-selective chiral analysis are reviewed. The first is based on the formation of diastereomers that are of homo- and hetero- type with respect to the enantiomers of involved chiral molecules. This way is quite well-established with numerous applications. The other two ways are more recent developments, both based on circular dichroism (CD). In one, conventional or nonlinear electronic CD is linked to mass spectrometry (MS) by resonance-enhanced multiphoton ionization. The other is based on CD in the angular distribution of photoelectrons, which is measured in combination with MS via photoion photoelectron coincidence. Among the many important applications of mass-selective chiral analysis, this review focuses on its use as an analytical tool for the development of heterogeneous enantioselective chemical catalysis. There exist other approaches to combine chiral analysis and mass-selective detection, such as chiral chromatography MS, which are not discussed here.

Tuning the photon statistics of a strongly coupled nanophotonic system

NASA Astrophysics Data System (ADS)

Dory, Constantin; Fischer, Kevin A.; Müller, Kai; Lagoudakis, Konstantinos G.; Sarmiento, Tomas; Rundquist, Armand; Zhang, Jingyuan L.; Kelaita, Yousif; Sapra, Neil V.; Vučković, Jelena

2017-02-01

We investigate the dynamics of single- and multiphoton emission from detuned strongly coupled systems based on the quantum-dot-photonic-crystal resonator platform. Transmitting light through such systems can generate a range of nonclassical states of light with tunable photon counting statistics due to the nonlinear ladder of hybridized light-matter states. By controlling the detuning between emitter and resonator, the transmission can be tuned to strongly enhance either single- or two-photon emission processes. Despite the strongly dissipative nature of these systems, we find that by utilizing a self-homodyne interference technique combined with frequency filtering we are able to find a strong two-photon component of the emission in the multiphoton regime. In order to explain our correlation measurements, we propose rate equation models that capture the dominant processes of emission in both the single- and multiphoton regimes. These models are then supported by quantum-optical simulations that fully capture the frequency filtering of emission from our solid-state system.

Comparison of the Detection Characteristics of Trace Species Using Laser-Induced Breakdown Spectroscopy and Laser Breakdown Time-of-Flight Mass Spectrometry

PubMed Central

Wang, Zhenzhen; Deguchi, Yoshihiro; Yan, Junjie; Liu, Jiping

2015-01-01

The rapid and precise element measurement of trace species, such as mercury, iodine, strontium, cesium, etc. is imperative for various applications, especially for industrial needs. The elements mercury and iodine were measured by two detection methods for comparison of the corresponding detection features. A laser beam was focused to induce plasma. Emission and ion signals were detected using laser-induced breakdown spectroscopy (LIBS) and laser breakdown time-of-flight mass spectrometry (LB-TOFMS). Multi-photon ionization and electron impact ionization in the plasma generation process can be controlled by the pressure and pulse width. The effect of electron impact ionization on continuum emission, coexisting molecular and atomic emissions became weakened in low pressure condition. When the pressure was less than 1 Pa, the plasma was induced by laser dissociation and multi-photon ionization in LB-TOFMS. According to the experimental results, the detection limits of mercury and iodine in N2 were 3.5 ppb and 60 ppb using low pressure LIBS. The mercury and iodine detection limits using LB-TOFMS were 1.2 ppb and 9.0 ppb, which were enhanced due to different detection features. The detection systems of LIBS and LB-TOFMS can be selected depending on the condition of each application. PMID:25769051

Multi-photon EIT

NASA Astrophysics Data System (ADS)

Laarits, Toomas; O'Gorman, Bryan; Crescimanno, Michael

2008-03-01

We describe and solve a quantum optics models for multiphoton interrogation of an electromagnetically induced transparency (EIT) resonance. Multiphoton EIT, like its well studied Lambda-system EIT progenitor, is a generalization of the N-resonance process recently studied for atomic time keeping. The solution of these models allows a preliminary determination of this processes utility as the basis of a frequency standard.

Multiphoton dynamics of qutrits in the ultrastrong coupling regime with a quantized photonic field

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

Avetissian, H. K., E-mail: avetissian@ysu.am; Avetissian, A. K.; Mkrtchian, G. F.

2015-12-15

Multiphoton resonant excitation of a three-state quantum system (a qutrit) with a single-mode photonic field is considered in the ultrastrong coupling regime, when the qutrit–photonic field coupling rate is comparable to appreciable fractions of the photon frequency. For ultrastrong couplings, the obtained solutions of the Schrödinger equation that reveal multiphoton Rabi oscillations in qutrits with the interference effects leading to the collapse and revival of atomic excitation probabilities at the direct multiphoton resonant transitions.

O({sup 3}P{sub J}) formation and desorption by 157-nm photoirradiation of amorphous solid water

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

DeSimone, Alice J.; Orlando, Thomas M., E-mail: thomas.orlando@chemistry.gatech.edu; School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332–0400

2014-03-07

Photodissociation of amorphous solid water (ASW) deposited on a thinly oxidized copper substrate at 82 K was studied by measuring O({sup 3}P{sub J=2,1,0}) photoproducts detected with resonance-enhanced multiphoton ionization. For each spin-orbit state, the oxygen atom time-of-flight spectrum was measured as a function of H{sub 2}O exposure, which is related to ice thickness, and 157-nm irradiation time. Four Maxwell-Boltzmann distributions with translational temperatures of 10 000 K, 1800 K, 400 K, and 82 K were found to fit the data. The most likely formation mechanisms are molecular elimination following ionization of water and ion-electron recombination, secondary recombination of hydroxyl radicals, andmore » photodissociation of adsorbed hydroxyl radicals. Evidence for O-atom diffusion through bulk ASW was found for H{sub 2}O exposures of at least 5 Langmuir (1 L = 10{sup −6} Torr s). The cross sections for O({sup 3}P{sub 2}) depletion were 1.3 × 10{sup −19} and 6.5 × 10{sup −20} cm{sup 2} for 1 and 5 L, respectively.« less

Spatial Characterization of Polycyclic Aromatic Hydrocarbons in 2008 TC3 Samples

NASA Astrophysics Data System (ADS)

Sabbah, Hassan; Morrow, A.; Zare, R. N.; Jenniskens, P.

2009-09-01

Hassan Sabbah1, Amy L. Morrow1, Richard N. Zare1 and Petrus Jenniskens2 1Stanford University, Stanford, California 94305, 2 SETI Institute, Carl Sagan Center, 515 North Whisman Road, Mountain View, California 94043, USA. In October 2006 a small asteroid (2-3 meters) was observed in outer space. On October 7, 2008, it entered the Earth's atmosphere creating a fireball over Northern Sudan. Some 280 meteorites were collected by the University of Khartoum. In order to explore the existence of organic materials, specifically polycyclic aromatic hydrocarbons (PAHs), we applied two-step laser desorption laser ionization mass spectrometry (L2MS) to some selected fragments. This technique consists of desorbing with a pulsed infrared laser beam the solid materials into a gaseous phase with no fragmentation followed by resonance enhanced multiphoton ionization to analyze the PAH content. L2MS was already applied to an array of extraterrestrial objects including interplanetary dust particles IDPs, carbonaceous chondrites and comet coma particles. Moreover, spatial resolution of PAHs in 2008 TC3 samples was achieved to explore the heterogeneity within individual fragments. The results of these studies and their contribution to understanding the formation of this asteroid will be discussed.

Photochemical and Spectroscopic Effects Resulting from Excimer Laser Excitation.

NASA Astrophysics Data System (ADS)

Wang, Xuan Xiao

I. Photochemical production of ozone from pure oxygen using excimer lasers. Production of ozone was observed from experiments when oxygen was under a broadband pulsed KrF laser radiation. The production process was found to be autocatalytic. Mechanisms for the ozone formation were proposed. Experimental results over a range of oxygen pressure and laser pulse energy (irradiance) provided evidences in favor of the proposed mechanisms. Experiments were also numerically modeled. Good agreement between the experimental and the numerical results were observed, which provided further evidence to support the proposed mechanisms. Cross sections for some photochemical processes in the mechanisms were estimated. Production of ozone from pure oxygen under a ArF excimer laser radiation (193 nm) was also studied and numerically modeled. Effects of ambient water vapor on ozone production were investigated. Experimental results showed a fast ozone destruction when water vapor was present in the cell. However, numerical results obtained from the well-known OH and HO _2 chain ozone destruction mechanism predicted a slower ozone destruction. Possible reasons for the discrepancy are discussed. II. Resonance-enhanced multiphoton ionization of N_2 at 193 and 248 nm detected by N_sp{2}{+} fluorescence. Using a broadband excimer laser operating at 193 and 248 nm multiphoton ionization at high pressures in air and pure nitrogen has been detected by fluorescence from N_sp{2}{+} in the B-X firstnegative system. Measurements of the fluorescence intensity as a function of beam irradiance indicate resonance in N_2 at the energy of two 193 nm photons (2 + 1 REMPI) and three 248 nm photons (3 + 1 REMPI). Possible intermediate states are discussed. III. Excimer laser-induced fluorescence from some organic solvents. Fluorescence was observed from vapor phase benzene, toluene, p-xylene, benzyl chloride, methyl benzoate, acetic anhydride, ether, methanol, ethyl acetone, acetone, and 2-butanone using a broadband excimer laser operating at 248 nm and 308 nm as the source of excitation. Absolute fluorescence quantum yields for the substances under study were measured at 248 nm using toluene as the fluorescence standard. Fluorescence spectra from species produced from nonlinear photochemical processes were also studied.

Structural characterization of arginine-vasopressin and lysine-vasopressin by Fourier- transform ion cyclotron resonance mass spectrometry and infrared multiphoton dissociation.

PubMed

Bianco, Giuliana; Battista, Fabio; Buchicchio, Alessandro; Amarena, Concetta G; Schmitt-Kopplin, Philippe; Guerrieri, Antonio

2015-01-01

Arginine-vasopressin (AVP) and lysine-vasopressin (LVP) were analyzed by reversed-phase liquid chromatography/mass spectrometry (LC-MS) using Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) electrospray ionization (ESI) in the positive ion mode. LVP and AVP exhibited the protonated adduct [M+H](+) as the predominant ion at m/z 1056.43965 and at m/z 1084.44561, respectively. Infrared multiphoton dissociation (IRMPD), using a CO(2) laser source at a wavelength of 10.6 μm, was applied to protonated vasopressin molecules. The IRMPD mass spectra presented abundant mass fragments essential for a complete structural information. Several fragment ions, shared between two target molecules, are discussed in detail. Some previously unpublished fragments were identified unambiguously utilizing the high resolution and accurate mass information provided by the FT-ICR mass spectrometer. The opening of the disulfide loop and the cleavage of the peptide bonds within the ring were observed even under low-energy fragmentation conditions. Coupling the high-performance FT-ICR mass spectrometer with IRMPD as a contemporary fragmentation technique proved to be very promising for the structural characterization of vasopressin.

Development of injector/amplifier XUV lasers and initial studies of ultrashort pulse UV multiphoton ionization

NASA Astrophysics Data System (ADS)

Key, Michael H.; Blyth, W. J.; Cairns, Gerald F.; Damerell, A. R.; Dangor, A. E.; Danson, Colin N.; Evans, J. M.; Hirst, Graeme J.; Holden, M.; Hooker, Chris J.; Houliston, J. R.; Krishnan, J.; Lewis, Ciaran L. S.; Lister, J. M. D.; MacPhee, Andrew G.; Najmudin, Z.; Neely, David; Norreys, Peter A.; Offenberger, Allen A.; Osvay, Karoly; Pert, Geoffrey J.; Preston, S. G.; Ramsden, Stuart A.; Ross, Ian N.; Sibbett, Wilson; Tallents, Gregory J.; Smith, C.; Wark, Justin S.; Zhang, Jie

1994-02-01

An injector-amplifier architecture for XUV lasers has been developed and demonstrated using the Ge XXIII collisional laser. Results are described for injection into single and double plasma amplifiers. Prismatic lens-like and higher order aberrations in the amplifier are considered. Limitations on ultimate brightness are discussed and also scaling to operation at shorter wavelengths. A preliminary study has been made of UV multiphoton ionization using 300 fs pulses at high intensity.

Correlated electron and nuclear dynamics in strong field photoionization of H(2)(+).

PubMed

Silva, R E F; Catoire, F; Rivière, P; Bachau, H; Martín, F

2013-03-15

We present a theoretical study of H(2)(+) ionization under strong IR femtosecond pulses by using a method designed to extract correlated (2D) photoelectron and proton kinetic energy spectra. The results show two distinct ionization mechanisms-tunnel and multiphoton ionization-in which electrons and nuclei do not share the energy from the field in the same way. Electrons produced in multiphoton ionization share part of their energy with the nuclei, an effect that shows up in the 2D spectra in the form of energy-conservation fringes similar to those observed in weak-field ionization of diatomic molecules. In contrast, tunneling electrons lead to fringes whose position does not depend on the proton kinetic energy. At high intensity, the two processes coexist and the 2D plots show a very rich behavior, suggesting that the correlation between electron and nuclear dynamics in strong field ionization is more complex than one would have anticipated.

Observation of novel photochemistry in the multiphoton ionization of Mo(CO) sub 6 van der Waals clusters

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

Peifer, W.R.; Garvey, J.F.

1989-07-27

van der Waals clusters of Mo(CO){sub 6} generated in the free-jet expansion of a pulsed beam of seeded helium are subjected to multiphoton ionization and the product ions analyzed by quadrupole mass spectrometry. Oxomolybdenum and dioxomolybdenum ions are observed to be produced with high efficiency. This behavior is in striking contrast to that of metal carbonyl monomers and covalently bound cluster carbonyls, which under complete ligand loss prior to ionization. The observed photochemistry is ascribed to reactions between a photoproduced molybdenum atom and the ligands of neighboring Mo(CO){sub 6} solvent molecules within the van der Waals cluster.

USE OF REMPI-TOFMS FOR REAL-TIME MEASUREMENT OF TRACE AROMATICS DURING OPERATION OF AIRCRAFT GROUND EQUIPMENT

EPA Science Inventory

Emissions of aromatic air toxics from aircraft ground equipment were measured with a resonance enhanced multiphoton ionization—time of flight mass spectrometry (REMPI-TOFMS) system consisting of a pulsed solid state laser for photoionization and a TOFMS for mass discrimination. T...

Application of Laser Mass Spectrometry to Art and Archaeology

NASA Technical Reports Server (NTRS)

Gulian, Lase Lisa E.; Callahan, Michael P.; Muliadi, Sarah; Owens, Shawn; McGovern, Patrick E.; Schmidt, Catherine M.; Trentelman, Karen A.; deVries, Mattanjah S.

2011-01-01

REMPI laser mass spectrometry is a combination of resonance enhanced multiphoton ionization spectroscopy and time of flight mass spectrometry, This technique enables the collection of mass specific optical spectra as well as of optically selected mass spectra. Analytes are jet-cooled by entrainment in a molecular beam, and this low temperature gas phase analysis has the benefit of excellent vibronic resolution. Utilizing this method, mass spectrometric analysis of historically relevant samples can be simplified and improved; Optical selection of targets eliminates the need for chromatography while knowledge of a target's gas phase spectroscopy allows for facile differentiation of molecules that are in the aqueous phase considered spectroscopically indistinguishable. These two factors allow smaller sample sizes than commercial MS instruments, which in turn will require less damage to objects of antiquity. We have explored methods to optimize REMPI laser mass spectrometry as an analytical tool to archaeology using theobromine and caffeine as molecular markers in Mesoamerican pottery, and are expanding this approach to the field of art to examine laccaic acid in shellacs.

High-precision laser spectroscopy of the CO A(1)Π - X(1)Σ(+) (2,0), (3,0), and (4,0) bands.

PubMed

Niu, M L; Ramirez, F; Salumbides, E J; Ubachs, W

2015-01-28

High-precision two-photon Doppler-free frequency measurements have been performed on the CO A(1)Π - X(1)Σ(+) fourth-positive system (2,0), (3,0), and (4,0) bands. Absolute frequencies of forty-three transitions, for rotational quantum numbers up to J = 5, have been determined at an accuracy of 1.6 × 10(-3) cm(-1), using advanced techniques of two-color 2  +  1' resonance-enhanced multi-photon ionization, Sagnac interferometry, frequency-chirp analysis on the laser pulses, and correction for AC-Stark shifts. The accurate transition frequencies of the CO A(1)Π - X(1)Σ(+) system are of relevance for comparison with astronomical data in the search for possible drifts of fundamental constants in the early universe. The present accuracies in laboratory wavelengths of Δλ/λ = 2 × 10(-8) may be considered exact for the purpose of such comparisons.

Initiation of air ionization by ultrashort laser pulses: evidence for a role of metastable-state air molecules

NASA Astrophysics Data System (ADS)

Bulgakov, A. V.; Mirza, I.; Bulgakova, N. M.; Zhukov, V. P.; Machulka, R.; Haderka, O.; Campbell, E. E. B.; Mocek, T.

2018-06-01

Transmission measurements for femtosecond laser pulses focused in air with spectral analysis of emission from the focal region have been carried out for various pulse energies and air pressures. The air breakdown threshold and pulse attenuation due to plasma absorption are evaluated and compared with calculations based on the multiphoton ionization model. The plasma absorption is found to depend on the pulse repetition rate and is considerably stronger at 1 kHz than at 1–10 Hz. This suggests that accumulation of metastable states of air molecules plays an important role in initiation of air breakdown, enhancing the ionization efficiency at high repetition rates. Possible channels of metastable-state-assisted air ionization and the role of the observed accumulation effect in laser material processing are discussed.

Detection of gaseous compounds by needle trap sampling and direct thermal-desorption photoionization mass spectrometry: concept and demonstrative application to breath gas analysis.

PubMed

Kleeblatt, Juliane; Schubert, Jochen K; Zimmermann, Ralf

2015-02-03

A fast detection method to analyze gaseous organic compounds in complex gas mixtures was developed, using a needle trap device (NTD) in conjunction with thermal-desorption photoionization time-of-flight mass spectrometry (TD-PI-TOFMS). The mass spectrometer was coupled via a deactivated fused silica capillary to an injector of a gas chromatograph. In the hot injector, the analytes collected on the NTD were thermally desorbed and directly transferred to the PI-TOFMS ion source. The molecules are softly ionized either by single photon ionization (SPI, 118 nm) or by resonance enhanced multiphoton ionization (REMPI, 266 nm), and the molecular ion signals are detected in the TOF mass analyzer. Analyte desorption and the subsequent PI-TOFMS detection step only lasts ten seconds. The specific selectivity of REMPI (i.e., aromatic compounds) and universal ionization characteristics render PI-MS as a promising detection system. As a first demonstrative application, the alveolar phase breath gas of healthy, nonsmoking subjects was sampled on NTDs. While smaller organic compounds such as acetone, acetaldehyde, isoprene, or cysteamine can be detected in the breath gas with SPI, REMPI depicts the aromatic substances phenol and indole at 266 nm. In the breath gas of a healthy, smoking male subject, several xenobiotic substances such as benzene, toluene, styrene, and ethylbenzene can be found as well. Furthermore, the NTD-REMPI-TOFMS setup was tested for breath gas taken from a mechanically ventilated pig under continuous intravenous propofol (2,6-diisopropylphenol, narcotic drug) infusion.

Spin Multiphoton Antiresonance at Finite Temperatures

NASA Astrophysics Data System (ADS)

Hicke, Christian; Dykman, Mark

2007-03-01

Weakly anisotropic S>1 spin systems display multiphoton antiresonance. It occurs when an Nth overtone of the radiation frequency coincides with the distance between the ground and the Nth excited energy level (divided by ). The coherent response of the spin displays a sharp minimum or maximum as a function of frequency, depending on which state was initially occupied. We find the spectral shape of the response dips/peaks. We also study the stationary response for zero and finite temperatures. The response changes dramatically with increasing temperature, when excited states become occupied even in the absence of radiation. The change is due primarily to the increasing role of single-photon resonances between excited states, which occur at the same frequencies as multiphoton resonances. Single-photon resonances are broad, because the single-photon Rabi frequencies largely exceed the multi-photon ones. This allows us to separate different resonances and to study their spectral shape. We also study the change of the spectrum due to relaxational broadening of the peaks, with account taken of both decay and phase modulation.

Reaction dynamics of Al + O₂ → AlO + O studied by a crossed-beam velocity map imaging technique: vib-rotational state selected angular-kinetic energy distribution.

PubMed

Honma, Kenji; Miyashita, Kazuki; Matsumoto, Yoshiteru

2014-06-07

Oxidation reaction of a gas-phase aluminum atom by a molecular oxygen was studied by a crossed-beam condition at 12.4 kJ/mol of collision energy. A (1+1) resonance-enhanced multiphoton ionization (REMPI) via the D(2)Σ(+)-X(2)Σ(+) transition of AlO was applied to ionize the product. The REMPI spectrum was analyzed to determine rotational state distributions for v = 0-2 of AlO. For several vib-rotational states of AlO, state selected angular and kinetic energy distributions were determined by a time-sliced ion imaging technique for the first time. Kinetic energy distributions were well represented by that taken into account initial energy spreads of collision energy and the population of the spin-orbit levels of the counter product O((3)P(J)) determined previously. All angular distributions showed forward and backward peaks, and the forward peaks were more pronounced than the backward one for the states of low internal energy. The backward peak intensity became comparable to the forward one for the states of high internal energy. These results and the rotational state distributions suggested that the reaction proceeds via an intermediate which has a lifetime comparable to or shorter than its rotational period.

Laser Ionization Studies of Hydrocarbon Flames.

NASA Astrophysics Data System (ADS)

Bernstein, Jeffrey Scott

Resonance-enhanced multiphoton ionization (REMPI) and laser induced fluorescence (LIF) are applied as laser based flame diagnostics for studies of hydrocarbon combustion chemistry. rm CH_4/O_2, C _2H_4/O_2, and rm C_2H_6/O_2 low pressure ( ~20 Torr), stoichiometric burner stabilized flat flames are studied. Density profiles of intermediate flame species, existing at ppm concentrations, are mapped out as a function of distance from the burner head. Profiles resulting from REMPI and LIF detection are obtained for HCO, CH_3, H, O, OH, CH, and CO flame radicals. The above flame systems are computer modeled against currently accepted combustion mechanisms using the Chemkin and Premix flame codes developed at Sandia National Laboratories. The modeled profile densities show good agreement with the experimental results of the CH_4/O_2 flame system, thus confirming the current C1 kinetic flame mechanism. Discrepancies between experimental and modeled results are found with the C2 flames. These discrepancies are partially amended by modifying the rate constant of the rm C_2H_3+rm O_2 to H_2CO + HCO reaction. The modeled results computed with the modified rate constant strongly suggest that the kinetics of several or possibly many reactions in the C2 mechanism need refinement.

Multi-photon transitions and Rabi resonance in continuous wave EPR.

PubMed

Saiko, Alexander P; Fedaruk, Ryhor; Markevich, Siarhei A

2015-10-01

The study of microwave-radiofrequency multi-photon transitions in continuous wave (CW) EPR spectroscopy is extended to a Rabi resonance condition, when the radio frequency of the magnetic-field modulation matches the Rabi frequency of a spin system in the microwave field. Using the non-secular perturbation theory based on the Bogoliubov averaging method, the analytical description of the response of the spin system is derived for all modulation frequency harmonics. When the modulation frequency exceeds the EPR linewidth, multi-photon transitions result in sidebands in absorption EPR spectra measured with phase-sensitive detection at any harmonic. The saturation of different-order multi-photon transitions is shown to be significantly different and to be sensitive to the Rabi resonance. The noticeable frequency shifts of sidebands are found to be the signatures of this resonance. The inversion of two-photon lines in some spectral intervals of the out-of-phase first-harmonic signal is predicted under passage through the Rabi resonance. The inversion indicates the transition from absorption to stimulated emission or vice versa, depending on the sideband. The manifestation of the primary and secondary Rabi resonance is also demonstrated in the time evolution of steady-state EPR signals formed by all harmonics of the modulation frequency. Our results provide a theoretical framework for future developments in multi-photon CW EPR spectroscopy, which can be useful for samples with long spin relaxation times and extremely narrow EPR lines. Copyright © 2015 Elsevier Inc. All rights reserved.

Comparison of the resonance-enhanced multiphoton ionization spectra of pyrrole and 2,5-dimethylpyrrole: Building toward an understanding of the electronic structure and photochemistry of porphyrins

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

Beames, Joseph M.; Nix, Michael G. D.; Hudson, Andrew J.

The photophysical properties of porphyrins have relevance for their use as light-activated drugs in cancer treatment and sensitizers in solid-state solar cells. However, the appearance of their UV-visible spectra is usually explained inadequately by qualitative molecular-orbital theories. We intend to gain a better insight into the intense absorption bands, and excited-state dynamics, that make porphyrins appropriate for both of these applications by gradually building toward an understanding of the macrocyclic structure, starting with studies of smaller pyrrolic subunits. We have recorded the (1+1) and (2+1) resonance-enhanced multiphoton ionization (REMPI) spectra of pyrrole and 2,5-dimethylpyrrole between 25 600 cm{sup -1} (390more » nm) and 48 500 cm{sup -1} (206 nm). We did not observe a (1+1) REMPI signal through the optically bright {sup 1}B{sub 2} ({pi}{pi}*) and {sup 1}A{sub 1} ({pi}{pi}*) states in pyrrole due to ultrafast deactivation via conical intersections with the dissociative {sup 1}A{sub 2} ({pi}{sigma}*) and {sup 1}B{sub 1} ({pi}{sigma}{sup *}) states. However, we did observe (2+1) REMPI through Rydberg states with a dominant feature at 27 432 cm{sup -1} (two-photon energy, 54 864 cm{sup -1}) assigned to a 3d(leftarrow){pi} transition. In contrast, 2,5-dimethylpyrrole has a broad and structured (1+1) REMPI spectrum between 36 000 and 42 500 cm{sup -1} as a result of vibronic transitions to the {sup 1}B{sub 2} ({pi}{pi}*) state, and it does not show the 3d(leftarrow){pi} Rydberg transition via (2+1) REMPI. We have complemented the experimental studies by a theoretical treatment of the excited states of both molecules using time-dependent density functional theory (TD-DFT) and accounted for the contrasting features in the spectra. TD-DFT modeled the photochemical activity of both the optically dark {sup 1}{pi}{sigma}* states (dissociative) and optically bright {sup 1}{pi}{pi}* states well, predicting the barrierless deactivation of the {sup 1}B{sub 2} ({pi}{pi}*) state of pyrrole and the bound minimum of the {sup 1}B{sub 2} ({pi}{pi}*) state in 2,5-dimethylpyrrole. However, the quantitative agreement between vibronic transition energies and the excited-state frequencies calculated by TD-DFT was hampered by inaccurate modeling of Rydberg orbital mixing with the valence states, caused by the lack of an asymptotic correction to the exchange-correlation functionals used.« less

Fast monitoring of motor exhaust components by resonant multi-photon ionisation and time-of-flight mass spectrometry

NASA Astrophysics Data System (ADS)

Franzen, Jochen; Frey, Rüdiger; Nagel, Holger

1995-03-01

A new analytical procedure is provided by the combination of two types of spectroscopy. Resonant ionization of selected compounds by multiphoton ionization is based on results of absorption spectroscopy for the compound molecules of interest and time-of-flight mass spectrometry serves for the unambigious detection of these compounds. An interesting application of this method is the fast exhaust gas analysis. In the development of future combustion engines, the management of dynamic motor processes becomes predominant because by more than 90 % of all the dangerous exhaust pollutions are produced in instationary motor phases such as fast speed or load changes. The investigation of dynamic processes however, requires fast analytical procedures with millisecond time resolution together with the capability to measure individual components in a very complex gas mixture The objectives for a development project of such an instrument were set by the Research Association for Combustion Engines (Forschungsvereinigung Verbrennungskraftmaschinen, FVV, Germany): Up to ten substances should be monitored synchroneously with a time resolution of about 10 milliseconds, with concentration limits of 1 part per million and with a precision better than 10 % relative standard deviation. Such a laser mass spectrometer for fast multi-component automotive exhaust analyses has been developed in a joint research project by Bruker-Franzen Analytik GmbH, Dornier GmbH and the Technical University of Munich. The system has been applied at a motor test facility to investigate the emissions of the aromatic hydrocarbons benzene, toluene and xylene, of nitric oxide and acetaldehyde in stationary and dynamic engine operation. These measurements demonstrate that strong emission of these pollutants takes place at instationary engine operation and in particular that these compounds are emitted at different times, giving new information about the processes in the combustion chamber and in the exhaust pipe.

Charge transfer and charge localization in extended radical cations: Investigation of model molecules for peptides

NASA Astrophysics Data System (ADS)

Weinkauf, Rainer; Lehrer, Florian

1998-12-01

Molecules consisting of a flexible tail and an aromatic chromophore are used as model systems to understand the situation of a single chromophore in a small peptide. Their S0-S1 resonant multiphoton ionization (REMPI) spectra show, that in neutral molecules the tail-chromophore interaction is weak and electronic excitation is localized at the chromophore. For molecules, where the ionization energy of the tail is considerable higher than that of the chromophore, by high resolution REMPI photoelectron spectroscopy we find the charge to be localized on the aromatic chromophore. This scheme also in suitable peptides allows local ionization at the aromatic chromophore. An estimate for various charge positions in peptide chains, however, shows, that for most of the amino acids electron hole positions in the nitrogen and oxygen "lone pair" orbitals of the peptide bond are nearly degenerate. REMPI photoelectron spectra of phenylethylamine, which as a model system contains such two degenerate charge positions, show small energetic shift of the ionization energy but strong geometry changes upon electron removal. This result is interpreted as direct ionization into a mixed charge delocalized state. Consequences for the charge transfer mechanism in peptides are discussed.

Ultrafast Electron Plasma Index: An Ionization Perspective

DTIC Science & Technology

2014-05-29

picture in mind, the derivation of the index was a combination of the principle of least action and Fermat’s principle. In the current textbook ...multiphoton ionization. Phys Rev Lett 71: 1994-1997. 27. Ivanov MY, Spanner M, Smirnova O (2005) Anatomy of strong field ionization. J. Mod.Phys 52

Detection of polychlorinated biphenyls in transformer oils in Vietnam by multiphoton ionization mass spectrometry using a far-ultraviolet femtosecond laser as an ionization source.

PubMed

Duong, Vu Thi Thuy; Duong, Vu; Lien, Nghiem Thi Ha; Imasaka, Tomoko; Tang, Yuanyuan; Shibuta, Shinpei; Hamachi, Akifumi; Hoa, Do Quang; Imasaka, Totaro

2016-03-01

Polychlorinated biphenyls (PCBs) in transformer and food oils were measured using gas chromatography combined with multiphoton ionization mass spectroscopy. An ultrashort laser pulse emitting in the far-ultraviolet region was utilized for efficient ionization of the analytes. Numerous signal peaks were clearly observed for a standard sample mixture of PCBs when the third and fourth harmonic emissions (267 and 200nm) of a femtosecond Ti:sapphire laser (800nm) were employed. The signal intensities were found to be greater when measured at 200nm compared with those measured at 267nm, providing lower detection limits especially for highly chlorinated PCBs at shorter wavelengths. After simple pretreatment using disposable columns, PCB congeners were measured and found to be present in the transformer oils used in Vietnam. Copyright © 2015 Elsevier B.V. All rights reserved.

Single and double multiphoton ionization of Li and Be atoms by strong laser fields

NASA Astrophysics Data System (ADS)

Telnov, Dmitry; Heslar, John; Chu, Shih-I.

2011-05-01

The time-dependent density functional theory with self-interaction correction and proper asymptotic long-range potential is extended for nonperturbative treatment of multiphoton single and double ionization of Li and Be atoms by strong 800 nm laser fields. We make use of the time-dependent Krieger-Li-Iafrate (TDKLI) exchange-correlation potential with the integer discontinuity which improves the description of the double ionization process. However, we have found that the discontinuity of the TDKLI potential is not sufficient to reproduce the characteristic feature of double ionization. This may happen because the discontinuity of the TDKLI potential is related to the spin particle numbers only and not to the total particle number. Introducing a discontinuity with respect to the total particle number to the exchange-correlation potential, we were able to obtain the knee structure in the intensity dependence of the double ionization probability of Be. This work was partially supported by DOE and NSF and by NSC-Taiwan.

Ultrafast multiphoton ionization dynamics and control of NaK molecules

NASA Astrophysics Data System (ADS)

Davidsson, Jan; Hansson, Tony; Mukhtar, Emad

1998-12-01

The multiphoton ionization dynamics of NaK molecules is investigated experimentally using one-color pump-probe femtosecond spectroscopy at 795 nm and intermediate laser field strengths (about 10 GW/cm2). Both NaK+ and Na+ ions are detected as a function of pulse separation time, pulse intensities, and strong pulse-weak pulse order. To aid in the analysis, the potential energy curves of the two lowest electronic states of NaK+ and the electronic transition dipole moment between them are calculated by the GAUSSIAN94 UCIS method. Different ionization pathways are identified by Franck-Condon analysis, and vibrational dynamics in the A 1Σ+ and 3 1Π states, as well as in the ground state, is observed. Further, the existence of a highly excited (above the adiabatic ionization limit) neutral state of NaK is proposed. By changing the strong pulse-weak pulse order of the pulses, the ionization pathways for production of both ions can be varied and thus controlled.

Modification of emission photon statistics from single quantum dots using metal/SiO2 core/shell nanostructures.

PubMed

Naiki, Hiroyuki; Oikawa, Hidetoshi; Masuo, Sadahiro

2017-04-12

Emission photon statistics, i.e., single-photon and multi-photon emissions, of isolated QDs is required for tailoring optoelectronic applications. In this article, we demonstrate that the emission photon statistics can be modified by the control of the spectral overlap of the QDs with the localized surface plasmon resonance (LSPR) of the metal nanoparticle (metal NP) and by the distance between the QD and the metal NP. Moreover, the contribution to the modification of the emission photon statistics, which is the excitation and emission enhancements and the quenching generated by the spectral overlap and the distance, is elucidated. By fabricating well-defined SiO 2 -coated AgNPs and AuNPs (metal/SiO 2 ), the spectral overlap originated from the metal species of Ag and Au and the distance constituted by the thickness of the SiO 2 shell are controlled. The probability of single-photon emission of single QD was increased by the enhancement of the excitation rate via adjusting the distance using Ag/SiO 2 while the single-photon emission was converted to multi-photon emission by the effect of exciton quenching at a short distance and a small spectral overlap. By contrast, the probability of multi-photon emission was increased by enhancement of the multi-photon emission rate and the quenching via the spectral overlap using Au/SiO 2 . These results indicated the fundamental finding to control emission photon statistics in single QDs by controlling the spectral overlap and the distance, and understand the interaction of plasmonic nanostructures and single QD systems.

Analysis of plasma-mediated ablation in aqueous tissue

NASA Astrophysics Data System (ADS)

Jiao, Jian; Guo, Zhixiong

2012-06-01

Plasma-mediated ablation using ultrafast lasers in transparent media such as aqueous tissues is studied. It is postulated that a critical seed free electron density exists due to the multiphoton ionization in order to trigger the avalanche ionization which causes ablation and during the avalanche ionization process the contribution of laser-induced photon ionization is negligible. Based on this assumption, the ablation process can be treated as two separate processes - the multiphoton and avalanche ionizations - at different time stages; so that an analytical solution to the evolution of plasma formation is obtained for the first time. The analysis is applied to plasma-mediated ablation in corneal epithelium and validated via comparison with experimental data available in the literature. The critical seed free-electron density and the time to initiate the avalanche ionization for sub-picosecond laser pulses are analyzed. It is found that the critical seed free-electron density decreases as the pulse width increases, obeying a tp-5.65 rule. This model is further extended to the estimation of crater size in the ablation of tissue-mimic polydimethylsiloxane (PDMS). The results match well with the available experimental measurements.

The dynamics of the Cl+C2H6→HCl(v',j')+C2H5 reaction at 0.24 eV: Is ethyl a spectator?

NASA Astrophysics Data System (ADS)

Bass, M. J.; Brouard, M.; Vallance, C.; Kitsopoulos, T. N.; Samartzis, P. C.; Toomes, R. L.

2003-10-01

The hydrogen atom abstraction reaction between Cl(2P3/2) and ethane has been studied at a mean collision energy of 0.24 eV. The experiments were performed in a coexpansion of molecular chlorine and ethane, with the atomic Cl reactants generated by laser photodissociation of Cl2 at 355 nm. HCl(v',j') products were detected quantum state selectively using (2+1) resonantly enhanced multiphoton ionization, coupled with velocity-map ion imaging. The ion images were used to determine center-of-mass angular and kinetic energy release distributions. Several analysis methods were employed and have been carefully assessed. It is shown that the single beam experiments can be used with confidence to determine both center-of-mass angular and energy release distributions. For the title reaction the angular distribution is found to be forward peaking, with on average 22% of the available energy channeled into internal excitation of the ethyl coproducts. Possible sources of this internal excitation are discussed.

Combined experimental and theoretical study of the benzocaine/Ar van der Waals system in supersonic expansions.

PubMed

León, Iker; Aguado, Edurne; Lesarri, Alberto; Fernández, José A; Castaño, Fernando

2009-02-12

The electronic spectra of Benzocaine x Ar(n), n = 0-4 were obtained using two-color resonance enhanced multiphoton ionization; the 1:1 and 1:2 clusters were investigated by ultraviolet/ultraviolet hole burning, stimulated emission pumping, and other laser spectroscopies. A single isomer was found for the 1:1 cluster, while two isomers of the 1:2 cluster were found: one with the two Ar atoms on the same side of the chromophore, and the other with the two Ar atoms sitting on opposite sides of the chromophore. The observed shifts point to the existence of a single isomer for the 1:3 and 1:4 species. Dissociation energies for the neutral ground and first excited electronic state and the ion ground electronic state of the complexes have been determined by the fragmentation threshold method and by ab initio calculations conducted at the MP2 level with 6-31++g(2d, p), 6-311++g(2d, p) and AUG-cc-pVTZ basis sets. The results are compared with those obtained for other similar systems.

Dynamics of the reactions of O(1D) with HCl, DCl, and Cl2

NASA Astrophysics Data System (ADS)

Matsumi, Yutaka; Tonokura, Kenichi; Kawasaki, Masahiro; Tsuji, Kazuhide; Obi, Kinichi

1993-05-01

The reactions O(1D)+HCl→OH+Cl (1a) and OCl+H (1b), O(1D)+DCl→OD+Cl (2a) and OCl+D (2b), and O(1D)+Cl2→OCl+Cl (3) are studied at an average collision energy of 7.6, 7.7, and 8.8 kcal/mol for (1), (2), and (3), respectively. H, D, and Cl atoms are detected by the resonance-enhanced multiphoton ionization technique. The average kinetic energies released to the products are estimated from Doppler profile measurements of the product atoms. The relative yields [OCl+H]/[OH+Cl] and [OCl+D]/[OD+Cl] are directly measured, and a strong isotope effect (H/D) on the relative yields is found. The fine-structure branding ratios [Cl(2P1/2]/[Cl(2P3/2)] of the reaction products are also measured. The results suggest that nonadiabatic couplings take place at the exit channels of the reactions (1a) and (2a), while the reaction (3) is totally adiabatic.

Collisional quenching of atoms and molecules on spacecraft thermal protection surfaces

NASA Technical Reports Server (NTRS)

Marinelli, W. J.; Green, B. D.

1988-01-01

Preliminary results of a research program to determine energy partitioning in spacecraft thermal protection materials due to atom recombination at the gas-surface interface are presented. The primary focus of the research is to understand the catalytic processes which determine heat loading on Shuttle, Aeroassisted OTV, and NASP thermal protection surfaces in nonequilibrium flight regimes. Highly sensitive laser diagnostics based on laser-induced fluorescence and resonantly-enhanced multiphoton ionization spectroscopy are used to detect atoms and metastable molecules. At low temperatures, a discharge flow reactor is employed to measure deactivation/recombination coefficients for O-atoms, N-atoms, and O2. Detection methods are presented for measuring O-atoms, O2 and N2, and results for deactivation of O2 and O-atoms on reaction-cured glass and Ni surfaces. Both atom recombination and metastable product formation are examined. Radio-frequency discharges are used to produce highly dissociated beams of atomic species at energies characteristic of the surface temperature. Auger electron spectroscopy is employed as a diagnostic of surface composition in order to accurately define and control measurement conditions.

On the properties of microsolvated molecules in the ground (S0) and excited (S1) states: The anisole-ammonia 1:1 complex

NASA Astrophysics Data System (ADS)

Biczysko, Malgorzata; Piani, Giovanni; Pasquini, Massimiliano; Schiccheri, Nicola; Pietraperzia, Giangaetano; Becucci, Maurizio; Pavone, Michele; Barone, Vincenzo

2007-10-01

State-of-the-art spectroscopic and theoretical methods have been exploited in a joint effort to elucidate the subtle features of the structure and the energetics of the anisole-ammonia 1:1 complex, a prototype of microsolvation processes. Resonance enhanced multiphoton ionization and laser-induced fluorescence spectra are discussed and compared to high-level first-principles theoretical models, based on density functional, many body second order perturbation, and coupled cluster theories. In the most stable nonplanar structure of the complex, the ammonia interacts with the delocalized π electron density of the anisole ring: hydrogen bonding and dispersive forces provide a comparable stabilization energy in the ground state, whereas in the excited state the dispersion term is negligible because of electron density transfer from the oxygen to the aromatic ring. Ground and excited state geometrical parameters deduced from experimental data and computed by quantum mechanical methods are in very good agreement and allow us to unambiguously determine the molecular structure of the anisole-ammonia complex.

Imaging spectroscopy of the missing REMPI bands of methyl radicals: Final touches on all vibrational frequencies of the 3p Rydberg states

NASA Astrophysics Data System (ADS)

Pan, Huilin; Liu, Kopin

2018-01-01

(2 + 1) resonance-enhanced multiphoton ionization (REMPI) detection of methyl radicals, in particular that via the intermediate 3p Rydberg states, has shown to be a powerful method and thus enjoyed a wide range of applications. Methyl has six vibrational modes. Among them—including partially and fully deuterated isotopologs—four out of twenty vibrational frequencies in the intermediate 3p states have so far eluded direct spectroscopic determination. Here, by exploiting the imaging spectroscopy approach to a few judiciously selected chemical reactions, the four long-sought REMPI bands—CHD2(611), CH2D(311), CH2D(511), and CH2D(611)—are discovered, which complete the REMPI identification for probing any vibrational mode of excitation of methyl radical and its isotopologs. These results, in conjunction with those previously reported yet scattered in the literature, are summarized here for ready reference, which should provide all necessary information for further spectral assignments and future studies of chemical dynamics using this versatile REMPI scheme.

Analytical model for atomic resonant attosecond transient absorption

NASA Astrophysics Data System (ADS)

Cariker, C.; Kjellson, T.; Lindroth, E.; Argenti, L.

2017-04-01

Recent advancements in ultrafast laser technology have made it possible to probe electron dynamics in highly excited atomic states that autoionize on a femtosecond timescale, thus giving insight into the dynamics of Auger decay and its interference with the continuum. These experiments provide a stringent test for time-resolved analytical models of autoionization. Here we present a finite-pulse, multi-photon perturbative model which is used in conjunction with ab-initio structure calculations to predict the attosecond transient absorption spectrum (ATAS) of an atom above the ionization threshold. We apply this model to compute the ATAS of argon in the vicinity of the 3s-1 4 p resonance as a function of the time delay between an extreme ultraviolet (XUV) and an infrared (IR) pulse, as well as of the angle between their polarization. We show that by modulating the parameters of the IR pulse it is possible to control the dipolar coupling between neighboring states and hence the lineshape of the 3s-1 4 p resonance. NSF Grant No. 1607588.

Revisiting photon-statistics effects on multiphoton ionization

NASA Astrophysics Data System (ADS)

Mouloudakis, G.; Lambropoulos, P.

2018-05-01

We present a detailed analysis of the effects of photon statistics on multiphoton ionization. Through a detailed study of the role of intermediate states, we evaluate the conditions under which the premise of nonresonant processes is valid. The limitations of its validity are manifested in the dependence of the process on the stochastic properties of the radiation and found to be quite sensitive to the intensity. The results are quantified through detailed calculations for coherent, chaotic, and squeezed vacuum radiation. Their significance in the context of recent developments in radiation sources such as the short-wavelength free-electron laser and squeezed vacuum radiation is also discussed.

Revisiting the relaxation dynamics of isolated pyrrole

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

Montero, Raúl; Ovejas, Virginia; Fernández-Fernández, Marta

Herein, the interpretation of the femtosecond-scale temporal evolution of the pyrrole ion signal, after excitation in the 267–217 nm interval, recently published by our group [R. Montero, A. Peralta Conde, V. Ovejas, M. Fernández-Fernández, F. Castaño, J. R. Vázquez de Aldana, and A. Longarte, J. Chem. Phys.137, 064317 (2012)] is re-visited. The observation of a shift in the pyrrole{sup +} transient respect to zero delay reference, initially attributed to ultrafast dynamics on the πσ{sup *} type state (3s a{sub 1} ← π 1a{sub 2}), is demonstrated to be caused by the existence of pump + probe populated states, along themore » ionization process. The influence of these resonances in pump-prone ionization experiments, when multi-photon probes are used, and the significance of a proper zero-time reference, is discussed. The possibility of preparing the πσ{sup *} state by direct excitation is investigated by collecting 1 + 1 photoelectron spectra, at excitation wavelengths ranging from 255 to 219 nm. No conclusive evidences of ionization through this state are found.« less

Probing Long-Range Configurations of Molecular Hydrogen

NASA Astrophysics Data System (ADS)

McCormack, Elizabeth

2011-05-01

Very long-range molecular configurations are of interest in a variety of contexts, for example, in the astro-chemistry of cold molecular clouds and in planetary atmospheres, including our own. Such states can be more than 10 times the size of the ground state and often possess energies above multiple ionization potentials and dissociation limits resulting in diverse and complex decay dynamics. Many of these configurations possess a double-well character arising from the interaction of molecular Rydberg states, repulsive doubly-excited states, and ionic states. The ion pair in hydrogen, an unusual molecular configuration consisting of one proton shrouded in a cloud of two electrons separated very far from the other proton, is notoriously difficult to create and study. We report results from on our investigation of such states using resonantly enhanced multi-photon ionization via the E,F v = 6, J = 0, 1, and 2 states to probe the H(n = 1) + H(n = 3) dissociation threshold energy region. Both molecular and atomic ion production were detected as a function of wavelength by using a time-of-flight mass spectrometer. Below threshold a series of highly excited vibrational levels of several long range states are observed. Above threshold broad resonances are observed with energies that agree well with the predictions of a mass-scaled Rydberg formula for bound states of the H+ H- ion pair. Measured linewidths, quantum defects, and rotational dependences are reported for ion pair principal quantum numbers in the range of n = 130 to 206. Our new results can be compared to recent experimental work using a different excitation scheme, which was the first spectroscopic observation of heavy Rydberg states in hydrogen, and new ab initio theoretical work. Supported by the National Science Foundation.

Atom-Resonant Heralded Single Photons by Interaction-Free Measurement

NASA Astrophysics Data System (ADS)

Wolfgramm, Florian; de Icaza Astiz, Yannick A.; Beduini, Federica A.; Cerè, Alessandro; Mitchell, Morgan W.

2011-02-01

We demonstrate the generation of rubidium-resonant heralded single photons for quantum memories. Photon pairs are created by cavity-enhanced down-conversion and narrowed in bandwidth to 7 MHz with a novel atom-based filter operating by “interaction-free measurement” principles. At least 94% of the heralded photons are atom-resonant as demonstrated by a direct absorption measurement with rubidium vapor. A heralded autocorrelation measurement shows gc(2)(0)=0.040±0.012, i.e., suppression of multiphoton contributions by a factor of 25 relative to a coherent state. The generated heralded photons can readily be used in quantum memories and quantum networks.

Electron and fluorescence spectra of a water molecule irradiated by an x-ray free-electron laser pulse

NASA Astrophysics Data System (ADS)

Schäfer, Julia M.; Inhester, Ludger; Son, Sang-Kil; Fink, Reinhold F.; Santra, Robin

2018-05-01

With the highly intense x-ray light generated by x-ray free-electron lasers (XFELs), molecular samples can be ionized many times in a single pulse. Here we report on a computational study of molecular spectroscopy at the high x-ray intensity provided by XFELs. Calculated photoelectron, Auger electron, and x-ray fluorescence spectra are presented for a single water molecule that reaches many electronic hole configurations through repeated ionization steps. The rich details shown in the spectra depend on the x-ray pulse parameters in a nonintuitive way. We discuss how the observed trends can be explained by the competition of microscopic electronic transition processes. A detailed comparison between spectra calculated within the independent-atom model and within the molecular-orbital framework highlights the chemical sensitivity of the spectral lines of multiple-hole configurations. Our results demonstrate how x-ray multiphoton ionization-related effects such as charge-rearrangement-enhanced x-ray ionization of molecules and frustrated absorption manifest themselves in the electron and fluorescence spectra.

Laser Pulse Width Dependence and Ionization Mechanism of Matrix-Assisted Laser Desorption/Ionization

NASA Astrophysics Data System (ADS)

Liang, Sheng-Ping; Lu, I.-Chung; Tsai, Shang-Ting; Chen, Jien-Lian; Lee, Yuan Tseh; Ni, Chi-Kung

2017-10-01

Ultraviolet laser pulses at 355 nm with variable pulse widths in the region from 170 ps to 1.5 ns were used to investigate the ionization mechanism of matrix-assisted laser desorption/ionization (MALDI) for matrices 2,5-dihydroxybenzoic acid (DHB), α-cyano-4-hydroxycinnamic acid (CHCA), and sinapinic acid (SA). The mass spectra of desorbed ions and the intensity and velocity distribution of desorbed neutrals were measured simultaneously for each laser shot. These quantities were found to be independent of the laser pulse width. A comparison of the experimental measurements and numerical simulations according to the multiphoton ionization, coupled photophysical and chemical dynamics (CPCD), and thermally induced proton transfer models showed that the predictions of thermally induced proton transfer model were in agreement with the experimental data, but those of the multiphoton ionization model were not. Moreover, the predictions of the CPCD model based on singlet-singlet energy pooling were inconsistent with the experimental data of CHCA and SA, but were consistent with the experimental data of DHB only when some parameters used in the model were adjusted to extreme values. [Figure not available: see fulltext.

Multiphoton ionization of many-electron atoms and highly-charged ions in intense laser fields: a relativistic time-dependent density functional theory approach

NASA Astrophysics Data System (ADS)

Tumakov, Dmitry A.; Telnov, Dmitry A.; Maltsev, Ilia A.; Plunien, Günter; Shabaev, Vladimir M.

2017-10-01

We develop an efficient numerical implementation of the relativistic time-dependent density functional theory (RTDDFT) to study multielectron highly-charged ions subject to intense linearly-polarized laser fields. The interaction with the electromagnetic field is described within the electric dipole approximation. The resulting time-dependent relativistic Kohn-Sham (RKS) equations possess an axial symmetry and are solved accurately and efficiently with the help of the time-dependent generalized pseudospectral method. As a case study, we calculate multiphoton ionization probabilities of the neutral argon atom and argon-like xenon ion. Relativistic effects are assessed by comparison of our present results with existing non-relativistic data.

Carrier-envelope-phase control of asymmetries in the multiphoton ionization of xenon atoms by ultrashort bichromatic fields

NASA Astrophysics Data System (ADS)

Kerbstadt, S.; Pengel, D.; Englert, L.; Bayer, T.; Wollenhaupt, M.

2018-06-01

We report on bichromatic multiphoton ionization of xenon atoms (Xe) to demonstrate carrier-envelope-phase (CEP) control of lateral asymmetries in the photoelectron momentum distribution. In the experiments, we employ a 4 f polarization pulse shaper to sculpture bichromatic fields with commensurable center frequencies ω1:ω2=7 :8 from an over-octave-spanning CEP-stable white light supercontinuum by spectral amplitude and phase modulation. The bichromatic fields are spectrally tailored to induce controlled interferences of 7- vs 8-photon quantum pathways in the 5 P3 /2 ionization continuum of Xe. The CEP sensitivity of the asymmetric final-state wave function arises from coherent superposition of continuum states with opposite parity. Our results demonstrate that shaper-generated bichromatic fields with tailored center frequency ratio are a suitable tool to localize CEP-sensitive asymmetries in a specific photoelectron kinetic-energy window.

Real-time analysis of aromatics in combustion engine exhaust by resonance-enhanced multiphoton ionisation time-of-flight mass spectrometry (REMPI-TOF-MS): a robust tool for chassis dynamometer testing.

PubMed

Adam, T W; Clairotte, M; Streibel, T; Elsasser, M; Pommeres, A; Manfredi, U; Carriero, M; Martini, G; Sklorz, M; Krasenbrink, A; Astorga, C; Zimmermann, R

2012-07-01

Resonance-enhanced multiphoton ionisation time-of-flight mass spectrometry (REMPI-TOF-MS) is a robust method for real-time analysis of monocyclic and polycyclic aromatic hydrocarbons in complex emissions. A mobile system has been developed which enables direct analysis on site. In this paper, we utilize a multicomponent calibration scheme based on the analytes' photo-ionisation cross-sections relative to a calibrated species. This allows semi-quantification of a great number of components by only calibrating one compound of choice, here toluene. The cross-sections were determined by injecting nebulised solutions of aromatic compounds into the TOF-MS ion source with the help of a HPLC pump. Then, REMPI-TOF-MS was implemented at various chassis dynamometers and test cells and the exhaust of the following vehicles and engines investigated: a compression ignition light-duty (LD) passenger car, a compression ignition LD van, two spark ignition LD passenger cars, 2 two-stroke mopeds, and a two-stroke engine of a string gas trimmer. The quantitative time profiles of benzene are shown. The results indicate that two-stroke engines are a significant source for toxic and cancerogenic compounds. Air pollution and health effects caused by gardening equipment might still be underestimated.

Far-UV photochemical bond cleavage of n-amyl nitrite: bypassing a repulsive surface.

PubMed

Minitti, Michael P; Zhang, Yao; Rosenberg, Martin; Brogaard, Rasmus Y; Deb, Sanghamitra; Sølling, Theis I; Weber, Peter M

2012-01-19

We have investigated the deep-UV photoinduced, homolytic bond cleavage of amyl nitrite to form NO and pentoxy radicals. One-color multiphoton ionization with ultrashort laser pulses through the S(2) state resonance gives rise to photoelectron spectra that reflect ionization from the S(1) state. Time-resolved pump-probe photoionization measurements show that upon excitation at 207 nm, the generation of NO in the v = 2 state is delayed, with a rise time of 283 (16) fs. The time-resolved mass spectrum shows the NO to be expelled with a kinetic energy of 1.0 eV, which is consistent with dissociation on the S(1) state potential energy surface. Combined, these observations show that the first step of the dissociation reaction involves an internal conversion from the S(2) to the S(1) state, which is followed by the ejection of the NO radical on the predissociative S(1) state potential energy surface.

Multiphoton Ionization Mass and Photoelectron Spectroscopy.

DTIC Science & Technology

1984-07-01

tracted information about ion vibrational energy levels. Molecules studted include benzene, toluene, aniline, paradifluorobenzene, nitric oxide ...molecules or subgroups and not to others. Ion specific electrodes play an analogous role in electro - chemistry. The prospect of selectively ionizing a... acetaldehyde and butyraldehyde have been studied at the KrF and ArF laser wavelengths. Their ionization potentials are 10.2 and 9.8 eV, respectively

The Ar-NO van der Waals complex studied by resonant multiphoton ionization spectroscopy involving photoion and photoelectron measurements

NASA Astrophysics Data System (ADS)

Sato, Kenji; Achiba, Yohji; Kimura, Katsumi

1984-07-01

Using a 5% mixture of NO in Ar in a supersonic free jet, in the present work we have carried out measurements of the total ion current in the 380-385 nm laser wavelength region. We have also measured photoelectron kinetic energy spectra at individual ion current peaks. In the ion-current spectrum we have observed a new vibrational progression which consists of four peaks in the wavelength region longer than the peak of the two-photon transition of the free NO molecule NO(X, v″=0) →2hν NO(C,v'=0). It has been concluded that the new ion-current peaks are attributed to bound-to-bound transitions of the Ar-NO van der Waals complex from its ground state to the two-photon resonant state expressed by Ar-NO*(C 2Π, v'=0), in which the NO component is in the 3p Rydberg state. The whole resonant ionization process studied may be expressed by Ar-NO(X, v″=0) →2hνAr-NO*(C, v'=0) →hν Ar-NO+(X, v+=0). Each ion-current peak separation is about 50 cm-1, which may correspond to the frequency of the Ar-NO intermolecular stretching vibration, showing a strong anharmonicity. The dissociation energy (D0) of the Ar-NO*(C 2Π) state has been found to be 0.055±0.001 eV. From the photoelectron spectra, we also conclude that the adiabatic ionization energy of Ar-NO is Ia =9.148±0.005 eV and the dissociation energy of the Ar-NO+(X 1Σ) ion is D0=0.129±0.005 eV.

Probing cis-trans isomerization in the S{sub 1} state of C{sub 2}H{sub 2} via H-atom action and hot band-pumped IR-UV double resonance spectroscopies

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

Changala, P. Bryan; Baraban, Joshua H.; Field, Robert W., E-mail: rwfield@mit.edu

2015-08-28

We report novel experimental strategies that should prove instrumental in extending the vibrational and rotational assignments of the S{sub 1} state of acetylene, C{sub 2}H{sub 2}, in the region of the cis-trans isomerization barrier. At present, the assignments are essentially complete up to ∼500 cm{sup −1} below the barrier. Two difficulties arise when the assignments are continued to higher energies. One is that predissociation into C{sub 2}H + H sets in roughly 1100 cm{sup −1} below the barrier; the resulting quenching of laser-induced fluorescence (LIF) reduces its value for recording spectra in this region. The other difficulty is that tunnelingmore » through the barrier causes a staggering in the K-rotational structure of isomerizing vibrational levels. The assignment of these levels requires data for K values up to at least 3. Given the rotational selection rule K′ − ℓ{sup ′′} = ± 1, such data must be obtained via excited vibrational levels of the ground state with ℓ{sup ′′} > 0. In this paper, high resolution H-atom resonance-enhanced multiphoton ionization spectra are demonstrated to contain predissociated bands which are almost invisible in LIF spectra, while preliminary data using a hyperthermal pulsed nozzle show that ℓ{sup ′′} = 2 states can be selectively populated in a jet, giving access to K′ = 3 states in IR-UV double resonance.« less

An engineered CARS substrate with giant field enhancement in crisscross dimer nanostructure.

PubMed

Zhang, Jia; Chen, Shu; Wang, Junqiao; Mu, Kaijun; Fan, Chunzhen; Liang, Erjun; Ding, Pei

2018-01-15

We theoretically investigate the optical properties of a nanostructure consisting of the two identical and symmetrically arranged crisscrosses. A plasmonic Fano resonance is induced by a strong interplay between bright mode and dark modes, where the bright mode is due to electric dipole resonance while dark modes originate from the magnetic dipole induced by LC resonances. In this article, we find that the electric field "hotspots" corresponding to three different wavelengths can be positioned at the same spatial position, and its spectral tunability is achieved by changing geometric parameters. The crisscrosses system can be designed as a plasmonic substrate for enhancing Coherent Anti-Stokes Raman Scattering (CARS) signal. This discovery provides a new method to achieve single molecule detection. At the same time, it also has many important applications for multi-photon imaging and other nonlinear optical processes, such as four-wave mixing and stimulated Raman scattering.

Photofragment slice imaging studies of pyrrole and the Xe{center_dot}{center_dot}{center_dot}pyrrole cluster

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

Rubio-Lago, L.; Zaouris, D.; Sakellariou, Y.

The photolysis of pyrrole has been studied in a molecular beam at wavelengths of 250, 240, and 193.3 nm, using two different carrier gases, He and Xe. A broad bimodal distribution of H-atom fragment velocities has been observed at all wavelengths. Near threshold at both 240 and 250 nm, sharp features have been observed in the fast part of the H-atom distribution. Under appropriate molecular beam conditions, the entire H-atom loss signal from the photolysis of pyrrole at both 240 and 250 nm (including the sharp features) disappear when using Xe as opposed to He as the carrier gas. Wemore » attribute this phenomenon to cluster formation between Xe and pyrrole, and this assumption is supported by the observation of resonance enhanced multiphoton ionization spectra for the (Xe{center_dot}{center_dot}{center_dot}pyrrole) cluster followed by photofragmentation of the nascent cation cluster. Ab initio calculations are presented for the ground states of the neutral and cationic (Xe{center_dot}{center_dot}{center_dot}pyrrole) clusters as a means of understanding their structural and energetic properties.« less

Angular distributions for the inelastic scattering of NO(X2Π ) with O2(X3Σg-)

NASA Astrophysics Data System (ADS)

Brouard, M.; Gordon, S. D. S.; Nichols, B.; Squires, E.; Walpole, V.; Aoiz, F. J.; Stolte, S.

2017-05-01

The inelastic scattering of NO(X2Π ) by O2(X3Σg-) was studied at a mean collision energy of 550 cm-1 using velocity-map ion imaging. The initial quantum state of the NO(X2Π , v = 0, j = 0.5, Ω =0.5 , 𝜖 = -1 , f) molecule was selected using a hexapole electric field, and specific Λ-doublet levels of scattered NO were probed using (1 +1' ) resonantly enhanced multiphoton ionization. A modified "onion-peeling" algorithm was employed to extract angular scattering information from the series of "pancaked," nested Newton spheres arising as a consequence of the rotational excitation of the molecular oxygen collision partner. The extracted differential cross sections for NO(X) f →f and f →e Λ-doublet resolved, spin-orbit conserving transitions, partially resolved in the oxygen co-product rotational quantum state, are reported, along with O2 fragment pair-correlated rotational state population. The inelastic scattering of NO with O2 is shown to share many similarities with the scattering of NO(X) with the rare gases. However, subtle differences in the angular distributions between the two collision partners are observed.

REAL-TIME MONITORING OF DIOXINS AND OTHER ...

EPA Pesticide Factsheets

This project is part of EPA's EMPACT program which was begun in 1998 and is jointly administered by EPA's Office of Research and Development, the National Center for Environmental Research and Quality Assurance (NCERQA), and the National Center for Environmental Assessment. The program was developed to provide understandable environmental information on various research initiatives to the public in a timely manner on various issues of importance. This particular project involves development of the application of an on-line, real time, trace organic air toxic monitor, with special emphasis on dioxin-related compounds. Research efforts demonstrate the utility and usefulness of the Resonance Enhanced Multi-Photon Ionization (REMPI) analytical method for trace organics control, monitoring, and compliance assurance. Project objectives will be to develop the REMPI instrumental method into a tool that will be used for assessment of potential dioxin sources, control and prevention of dioxin formation in known sources, and communication of facility performance. This will be accomplished through instrument development, laboratory verification, thermokinetic modelling, equilibrium modelling, statistical determinations, field validation, program publication and presentation, regulatory office support, and development of data communication/presentation procedures. For additional information on this EMPACT project, visit the website at http://www.epa.gov/appcdwww/crb/empa

Relaxation channels of multi-photon excited xenon clusters

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

Serdobintsev, P. Yu.; Melnikov, A. S.; Department of Physics, St. Petersburg State University, Saint Petersburg 198904

2015-09-21

The relaxation processes of the xenon clusters subjected to multi-photon excitation by laser radiation with quantum energies significantly lower than the thresholds of excitation of atoms and ionization of clusters were studied. Results obtained by means of the photoelectron spectroscopy method showed that desorption processes of excited atoms play a significant role in the decay of two-photon excited xenon clusters. A number of excited states of xenon atoms formed during this process were discovered and identified.

A graph-theoretical representation of multiphoton resonance processes in superconducting quantum circuits

DOE PAGES

Jooya, Hossein Z.; Reihani, Kamran; Chu, Shih-I

2016-11-21

We propose a graph-theoretical formalism to study generic circuit quantum electrodynamics systems consisting of a two level qubit coupled with a single-mode resonator in arbitrary coupling strength regimes beyond rotating-wave approximation. We define colored-weighted graphs, and introduce different products between them to investigate the dynamics of superconducting qubits in transverse, longitudinal, and bidirectional coupling schemes. In conclusion, the intuitive and predictive picture provided by this method, and the simplicity of the mathematical construction, are demonstrated with some numerical studies of the multiphoton resonance processes and quantum interference phenomena for the superconducting qubit systems driven by intense ac fields.

On-Demand Single Photons with High Extraction Efficiency and Near-Unity Indistinguishability from a Resonantly Driven Quantum Dot in a Micropillar.

PubMed

Ding, Xing; He, Yu; Duan, Z-C; Gregersen, Niels; Chen, M-C; Unsleber, S; Maier, S; Schneider, Christian; Kamp, Martin; Höfling, Sven; Lu, Chao-Yang; Pan, Jian-Wei

2016-01-15

Scalable photonic quantum technologies require on-demand single-photon sources with simultaneously high levels of purity, indistinguishability, and efficiency. These key features, however, have only been demonstrated separately in previous experiments. Here, by s-shell pulsed resonant excitation of a Purcell-enhanced quantum dot-micropillar system, we deterministically generate resonance fluorescence single photons which, at π pulse excitation, have an extraction efficiency of 66%, single-photon purity of 99.1%, and photon indistinguishability of 98.5%. Such a single-photon source for the first time combines the features of high efficiency and near-perfect levels of purity and indistinguishabilty, and thus opens the way to multiphoton experiments with semiconductor quantum dots.

Quantitative measurement of electron number in nanosecond and picosecond laser-induced air breakdown

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

Wu, Yue; Sawyer, Jordan C.; Su, Liu

2016-05-07

Here we present quantitative measurements of total electron numbers in laser-induced air breakdown at pressures ranging from atmospheric to 40 bar{sub g} by 10 ns and 100 ps laser pulses. A quantifiable definition for the laser-induced breakdown threshold is identified by a sharp increase in the measurable total electron numbers via dielectric-calibrated coherent microwave scattering. For the 10 ns laser pulse, the threshold of laser-induced breakdown in atmospheric air is defined as the total electron number of ∼10{sup 6}. This breakdown threshold decreases with an increase of pressure and laser photon energy (shorter wavelength), which is consistent with the theory of initialmore » multiphoton ionization and subsequent avalanche processes. For the 100 ps laser pulse cases, a clear threshold is not present and only marginal pressure effects can be observed, which is due to the short pulse duration leading to stronger multiphoton ionization and minimal collisional avalanche ionization.« less

Quantum description of the high-order harmonic generation in multiphoton and tunneling regimes

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

Perez-Hernandez, J. A.; Plaja, L.

2007-08-15

We employ a recently developed S-matrix approach [L. Plaja and J. A. Perez-Hernandez, Opt. Express 15, 3629 (2007)] to investigate the process of harmonic generation in tunnel and multiphoton ionization regimes. In contrast with most of the previous approaches, this model is developed without the stationary phase approximation and including the relevant continuum-continuum transitions. Therefore, it provides a full quantum description of the harmonic generation process in these two ionization regimes, with a good quantitative accuracy with the exact results of the time-dependent Schroedinger equation. We show how this model can be used to investigate the contribution of the electronicmore » population ionized at different times, thus giving a time-resolved description that, up to now, was reserved only to semiclassical models. In addition, we will show some aspects of harmonic generation beyond the semiclassical predictions as, for instance, the emission of radiation while the electron is leaving the parent ion and the generation of harmonics in semiclassically forbidden situations.« less

Spectroscopic study on deuterated benzenes. III. Vibronic structure and dynamics in the S1 state

NASA Astrophysics Data System (ADS)

Kunishige, Sachi; Katori, Toshiharu; Kawabata, Megumi; Yamanaka, Takaya; Baba, Masaaki

2015-12-01

We observed the fluorescence excitation spectra and mass-selected resonance enhanced multiphoton ionization (REMPI) excitation spectra for the 6 01 , 6 01 10 1 , and 6 01 10 2 bands of the S1←S0 transition of jet-cooled deuterated benzene and assigned the vibronic bands of C6D6 and C6HD5. The 60 1 10 n (n = 0, 1, 2) and 00 0 transition energies were found to be dependent only on the number of D atoms (ND), which was reflected by the zero-point energy of each H/D isotopomer. In some isotopomers some bands, such as those of out-of-plane vibrations mixed with 611n, make the spectra complex. These included the 611021n level or combination bands with ν12 which are allowed because of reduced molecular symmetry. From the lifetime measurements of each vibronic band, some enhancement of the nonradiative intramolecular vibrational redistribution (IVR) process was observed. It was also found that the threshold excess energy of "channel three" was higher than the 6112 levels, which were similar for all the H/D isotopomers. We suggest that the channel three nonradiative process could be caused mainly by in-plane processes such as IVR and internal conversion at the high vibrational levels in the S1 state of benzene, although the out-of-plane vibrations might contribute to some degree.

L. V. Keldysh’s “Ionization in the Field of a Strong Electromagnetic Wave” and modern physics of atomic interaction with a strong laser field

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

Fedorov, M. V., E-mail: fedorov@gmail.com

2016-03-15

Basic premises, approximations, and results of L.V. Keldysh’s 1964 work on multiphoton ionization of atoms are discussed, as well as its influence on the modern science of the interaction of atomic–molecular systems with a strong laser field.

Observations of the high vibrational levels of the B ' ' B ¯ 1 Σu + state of H2

NASA Astrophysics Data System (ADS)

Chartrand, A. M.; Duan, W.; Ekey, R. C.; McCormack, E. F.

2016-01-01

Double-resonance laser spectroscopy via the E F 1 Σg + , v ' = 6 , J ' = 0 -2 state was used to probe the high vibrational levels of the B ' ' B ¯ 1 Σu + state of molecular hydrogen. Resonantly enhanced multiphoton ionization spectra were recorded by detecting ion production as a function of energy using a time of flight mass spectrometer. New measurements of energies for the v = 51-66 levels for the B ' ' B ¯ state of H2 are reported, which, taken with previous results, span the v = 46-69 vibrational levels. Results for energy levels are compared to theoretical close-coupled calculations [L. Wolniewicz, T. Orlikowski, and G. Staszewska, J. Mol. Spectrosc. 238, 118-126 (2006)]. The average difference between the 84 measured energies and calculated energies is -3.8 cm-1 with a standard deviation of 5.3 cm-1. This level of agreement showcases the success of the theoretical calculations in accounting for the strong rovibronic mixing of the 1 Σu + and 1 Πu + states. Due to the ion-pair character of the outer well, the observed energies of the vibrational levels below the third dissociation limit smoothly connect with previously observed energies of ion-pair states above this limit. The results provide an opportunity for testing a heavy Rydberg multi-channel quantum defect analysis of the high vibrational states below the third dissociation limit.

Single-field slice-imaging with a movable repeller: photodissociation of N₂O from a hot nozzle.

PubMed

Harding, Dan J; Neugebohren, J; Grütter, M; Schmidt-May, A F; Auerbach, D J; Kitsopoulos, T N; Wodtke, A M

2014-08-07

We present a new photo-fragment imaging spectrometer, which employs a movable repeller in a single field imaging geometry. This innovation offers two principal advantages. First, the optimal fields for velocity mapping can easily be achieved even using a large molecular beam diameter (5 mm); the velocity resolution (better than 1%) is sufficient to easily resolve photo-electron recoil in (2 + 1) resonant enhanced multiphoton ionization of N2 photoproducts from N2O or from molecular beam cooled N2. Second, rapid changes between spatial imaging, velocity mapping, and slice imaging are straightforward. We demonstrate this technique's utility in a re-investigation of the photodissociation of N2O. Using a hot nozzle, we observe slice images that strongly depend on nozzle temperature. Our data indicate that in our hot nozzle expansion, only pure bending vibrations--(0, v2, 0)--are populated, as vibrational excitation in pure stretching or bend-stretch combination modes are quenched via collisional near-resonant V-V energy transfer to the nearly degenerate bending states. We derive vibrationally state resolved absolute absorption cross-sections for (0, v2 ≤ 7, 0). These results agree well with previous work at lower values of v2, both experimental and theoretical. The dissociation energy of N2O with respect to the O((1)D) + N2¹Σ(g)⁺ asymptote was determined to be 3.65 ± 0.02 eV.

Investigating multiphoton phenomena using nonlinear dynamics

NASA Astrophysics Data System (ADS)

Huang, Shu

Many seemingly simple systems can display extraordinarily complex dynamics which has been studied and uncovered through nonlinear dynamical theory. The leitmotif of this thesis is changing phase-space structures and their (linear or non-linear) stabilities by adding control functions (which act on the system as external perturbations) to the relevant Hamiltonians. These phase-space structures may be periodic orbits, invariant tori or their stable and unstable manifolds. One-electron systems and diatomic molecules are fundamental and important staging ground for new discoveries in nonlinear dynamics. In past years, increasing emphasis and effort has been put on the control or manipulation of these systems. Recent developments of nonlinear dynamical tools can provide efficient ways of doing so. In the first subtopic of the thesis, we are adding a control function to restore tori at prescribed locations in phase space. In the remainder of the thesis, a control function with parameters is used to change the linear stability of the periodic orbits which govern the processes in question. In this thesis, we report our theoretical analyses on multiphoton ionization of Rydberg atoms exposed to strong microwave fields and the dissociation of diatomic molecules exposed to bichromatic lasers using nonlinear dynamical tools. This thesis is composed of three subtopics. In the first subtopic, we employ local control theory to reduce the stochastic ionization of hydrogen atom in a strong microwave field by adding a relatively small control term to the original Hamiltonian. In the second subtopic, we perform periodic orbit analysis to investigate multiphoton ionization driven by a bichromatic microwave field. Our results show quantitative and qualitative agreement with previous studies, and hence identify the mechanism through which short periodic orbits organize the dynamics in multiphoton ionization. In addition, we achieve substantial time savings with this approach. In the third subtopic we extend our periodic orbit analysis to the dissociation of diatomic molecules driven by a bichromatic laser. In this problem, our results based on periodic orbit analysis again show good agreement with previous work, and hence promise more potential applications of this approach in molecular physics.

Multiphoton versus confocal high resolution z-sectioning of enhanced green fluorescent microtubules: increased multiphoton photobleaching within the focal plane can be compensated using a Pockels cell and dual widefield detectors.

PubMed

Drummond, D R; Carter, N; Cross, R A

2002-05-01

Multiphoton excitation was originally projected to improve live cell fluorescence imaging by minimizing photobleaching effects outside the focal plane, yet reports suggest that photobleaching within the focal plane is actually worse than with one photon excitation. We confirm that when imaging enhanced green fluorescent protein, photobleaching is indeed more acute within the multiphoton excitation volume, so that whilst fluorescence increases as predicted with the square of the excitation power, photobleaching rates increase with a higher order relationship. Crucially however, multiphoton excitation also affords unique opportunities for substantial improvements to fluorescence detection. By using a Pockels cell to minimize exposure of the specimen together with multiple nondescanned detectors we show quantitatively that for any particular bleach rate multiphoton excitation produces significantly more signal than one photon excitation confocal microscopy in high resolution Z-axis sectioning of thin samples. Both modifications are readily implemented on a commercial multiphoton microscope system.

Facile time-of-flight methods for characterizing pulsed superfluid helium droplet beams

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

He, Yunteng; Zhang, Jie; Li, Yang

2015-08-15

We present two facile time-of-flight (TOF) methods of detecting superfluid helium droplets and droplets with neutral dopants. Without an electron gun and with only a heated filament and pulsed electrodes, the electron impact ionization TOF mass spectrometer can resolve ionized helium clusters such as He{sub 2}{sup +} and He{sub 4}{sup +}, which are signatures of superfluid helium droplets. Without ionizing any helium atoms, multiphoton non-resonant laser ionization of CCl{sub 4} doped in superfluid helium droplets at 266 nm generates complex cluster ions of dopant fragments with helium atoms, including (He){sub n}C{sup +}, (He){sub n}Cl{sup +}, and (He){sub n}CCl{sup +}. Usingmore » both methods, we have characterized our cryogenic pulsed valve—the Even-Lavie valve. We have observed a primary pulse with larger helium droplets traveling at a slower speed and a rebound pulse with smaller droplets at a faster speed. In addition, the pickup efficiency of dopant is higher for the primary pulse when the nozzle temperature is higher than 13 K, and the total time duration of the doped droplet pulse is only on the order of 20 μs. These results stress the importance of fast and easy characterization of the droplet beam for sensitive measurements such as electron diffraction of doped droplets.« less

Generation of mechanical interference fringes by multi-photon counting

NASA Astrophysics Data System (ADS)

Ringbauer, M.; Weinhold, T. J.; Howard, L. A.; White, A. G.; Vanner, M. R.

2018-05-01

Exploring the quantum behaviour of macroscopic objects provides an intriguing avenue to study the foundations of physics and to develop a suite of quantum-enhanced technologies. One prominent path of study is provided by quantum optomechanics which utilizes the tools of quantum optics to control the motion of macroscopic mechanical resonators. Despite excellent recent progress, the preparation of mechanical quantum superposition states remains outstanding due to weak coupling and thermal decoherence. Here we present a novel optomechanical scheme that significantly relaxes these requirements allowing the preparation of quantum superposition states of motion of a mechanical resonator by exploiting the nonlinearity of multi-photon quantum measurements. Our method is capable of generating non-classical mechanical states without the need for strong single-photon coupling, is resilient against optical loss, and offers more favourable scaling against initial mechanical thermal occupation than existing schemes. Moreover, our approach allows the generation of larger superposition states by projecting the optical field onto NOON states. We experimentally demonstrate this multi-photon-counting technique on a mechanical thermal state in the classical limit and observe interference fringes in the mechanical position distribution that show phase super-resolution. This opens a feasible route to explore and exploit quantum phenomena at a macroscopic scale.

Fast detection of narcotics by single photon ionization mass spectrometry and laser ion mobility spectrometry

NASA Astrophysics Data System (ADS)

Laudien, Robert; Schultze, Rainer; Wieser, Jochen

2010-10-01

In this contribution two analytical devices for the fast detection of security-relevant substances like narcotics and explosives are presented. One system is based on an ion trap mass spectrometer (ITMS) with single photon ionization (SPI). This soft ionization technique, unlike electron impact ionization (EI), reduces unwanted fragment ions in the mass spectra allowing the clear determination of characteristic (usually molecular) ions. Their enrichment in the ion trap and identification by tandem MS investigations (MS/MS) enables the detection of the target substances in complex matrices at low concentrations without time-consuming sample preparation. For SPI an electron beam pumped excimer light source of own fabrication (E-Lux) is used. The SPI-ITMS system was characterized by the analytical study of different drugs like cannabis, heroin, cocaine, amphetamines, and some precursors. Additionally, it was successfully tested on-site in a closed illegal drug laboratory, where low quantities of MDMA could be directly detected in samples from floors, walls and lab equipments. The second analytical system is based on an ion mobility (IM) spectrometer with resonant multiphoton ionization (REMPI). With the frequency quadrupled Nd:YAG laser (266 nm), used for ionization, a selective and sensitive detection of aromatic compounds is possible. By application of suited aromatic dopants, in addition, also non-aromatic polar compounds are accessible by ion molecule reactions like proton transfer or complex formation. Selected drug precursors could be successfully detected with this device as well, qualifying it to a lower-priced alternative or useful supplement of the SPI-ITMS system for security analysis.

Strong field control of the interatomic Coulombic decay process in quantum dots

NASA Astrophysics Data System (ADS)

Haller, Anika; Chiang, Ying-Chih; Menger, Maximilian; Aziz, Emad F.; Bande, Annika

2017-01-01

In recent years the laser-induced interatomic Coulombic decay (ICD) process in paired quantum dots has been predicted (Bande, 2013). In this work we target the enhancement of ICD by scanning over a range of strong-field laser intensities. The GaAs quantum dots are modeled by a one-dimensional double-well potential in which simulations are done with the space-resolved multi-configuration time-dependent Hartree method including antisymmetrization to account for the fermions. As a novelty a complementary state-resolved ansatz is developed to consolidate the interpretation of transient state populations, widths obtained for the ICD and the competing direct ionization channel, and Fano peak profiles in the photoelectron spectra. The major results are that multi-photon processes are unimportant even for the strongest fields. Further, below- π to π pulses display the highest ICD efficiency while the direct ionization becomes less dominant.

Unified Time and Frequency Picture of Ultrafast Atomic Excitation in Strong Laser Fields

NASA Astrophysics Data System (ADS)

Zimmermann, H.; Patchkovskii, S.; Ivanov, M.; Eichmann, U.

2017-01-01

Excitation and ionization in strong laser fields lies at the heart of such diverse research directions as high-harmonic generation and spectroscopy, laser-induced diffraction imaging, emission of femtosecond electron bunches from nanotips, self-guiding, filamentation and mirrorless lasing during propagation of light in atmospheres. While extensive quantum mechanical and semiclassical calculations on strong-field ionization are well backed by sophisticated experiments, the existing scattered theoretical work aiming at a full quantitative understanding of strong-field excitation lacks experimental confirmation. Here we present experiments on strong-field excitation in both the tunneling and multiphoton regimes and their rigorous interpretation by time dependent Schrödinger equation calculations, which finally consolidates the seemingly opposing strong-field regimes with their complementary pictures. Most strikingly, we observe an unprecedented enhancement of excitation yields, which opens new possibilities in ultrafast strong-field control of Rydberg wave packet excitation and laser intensity characterization.

Zero kinetic energy photoelectron spectroscopy of triphenylene.

PubMed

Harthcock, Colin; Zhang, Jie; Kong, Wei

2014-06-28

We report vibrational information of both the first electronically excited state and the ground cationic state of jet-cooled triphenylene via the techniques of resonantly enhanced multiphoton ionization (REMPI) and zero kinetic energy (ZEKE) photoelectron spectroscopy. The first excited electronic state S1 of the neutral molecule is of A1' symmetry and is therefore electric dipole forbidden in the D3h group. Consequently, there are no observable Franck-Condon allowed totally symmetric a1' vibrational bands in the REMPI spectrum. All observed vibrational transitions are due to Herzberg-Teller vibronic coupling to the E' third electronically excited state S3. The assignment of all vibrational bands as e' symmetry is based on comparisons with calculations using the time dependent density functional theory and spectroscopic simulations. When an electron is eliminated, the molecular frame undergoes Jahn-Teller distortion, lowering the point group to C2v and resulting in two nearly degenerate electronic states of A2 and B1 symmetry. Here we follow a crude treatment by assuming that all e' vibrational modes resolve into b2 and a1 modes in the C2v molecular frame. Some observed ZEKE transitions are tentatively assigned, and the adiabatic ionization threshold is determined to be 63 365 ± 7 cm(-1). The observed ZEKE spectra contain a consistent pattern, with a cluster of transitions centered near the same vibrational level of the cation as that of the intermediate state, roughly consistent with the propensity rule. However, complete assignment of the detailed vibrational structure due to Jahn-Teller coupling requires much more extensive calculations, which will be performed in the future.

Multiple product pathways in photodissociation of nitromethane at 213 nm

NASA Astrophysics Data System (ADS)

Sumida, Masataka; Kohge, Yasunori; Yamasaki, Katsuyoshi; Kohguchi, Hiroshi

2016-02-01

In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π* transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH3, NO(X 2Π, A 2Σ+), and O(3PJ) photofragments. The rotationally state-resolved scattering distribution of the CH3 fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH3 fragment indicated the production of the NO2 counter-product in the electronic excited state, wherein 1 2B2 was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O(3PJ) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A 2Σ+) fragment, which was detected by ionization spectroscopy via the Rydberg ←A 2Σ+ transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH3 + NO2,CH3 + NO + O,CH3O + NO, and CH3NO + O, following the π → π* transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.

Multiple product pathways in photodissociation of nitromethane at 213 nm.

PubMed

Sumida, Masataka; Kohge, Yasunori; Yamasaki, Katsuyoshi; Kohguchi, Hiroshi

2016-02-14

In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π(*) transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH3, NO(X (2)Π, A (2)Σ(+)), and O((3)PJ) photofragments. The rotationally state-resolved scattering distribution of the CH3 fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH3 fragment indicated the production of the NO2 counter-product in the electronic excited state, wherein 1 (2)B2 was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O((3)PJ) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A (2)Σ(+)) fragment, which was detected by ionization spectroscopy via the Rydberg ← A (2)Σ(+) transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH3 + NO2,CH3 + NO + O,CH3O + NO, and CH3NO + O, following the π → π(*) transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.

Quantum statistics of four-wave mixing by a nonlinear resonant microcavity

NASA Astrophysics Data System (ADS)

Sherkunov, Y.; Whittaker, David M.; Schomerus, Henning; Fal'ko, Vladimir

2014-09-01

We analyze the correlation and spectral properties of two-photon states resonantly transmitted by a nonlinear optical microcavity. We trace the correlation properties of transmitted two-photon states to the decay spectrum of multiphoton resonances in the nonlinear microcavity.

Strong-field ionization of Li and Be: a time-dependent density functional theory with self-interaction correction

NASA Astrophysics Data System (ADS)

Telnov, Dmitry A.; Heslar, John T.; Chu, Shih-I.

2011-11-01

In the framework of the time-dependent density functional theory, we have performed 3D calculations of multiphoton ionization of Li and Be atoms by strong near-infrared laser fields. The results for the intensity-dependent probabilities of single and double ionization are presented. We make use of the time-dependent Krieger-Li-Iafrate exchange-correlation potential with self-interaction correction (TD-KLI-SIC). Such a potential possesses an integer discontinuity which improves description of the ionization process. However, we have found that the discontinuity of the TD-KLI-SIC potential is not sufficient to reproduce characteristic feature of double ionization.

An Automated System for the Control of, and Data Acquisition from Multiphoton Ionization and Fluorescence Lifetime Measurements.

DTIC Science & Technology

1986-09-01

Quanta- Ray company , which also supplied the laser used for the multiphoton work. The, burner was mounted on a translator stage from Velmex, Inc...and no longer exists as a process in the system. When the user analysis program has completed, the lifetime program is again automatically re-started...KCHAR) RETURN 100 FORMAT(I3) 101 FORMAT(F7.2) END SUBROUTINE LAB4 FODA SE"oteD C This routine puts the label "INTEGRAL FROM DATA SET" on the MDP C screen

Wavelength dependence of nanosecond infrared laser-induced breakdown in water: Evidence for multiphoton initiation via an intermediate state

NASA Astrophysics Data System (ADS)

Linz, Norbert; Freidank, Sebastian; Liang, Xiao-Xuan; Vogelmann, Hannes; Trickl, Thomas; Vogel, Alfred

2015-04-01

Investigation of the wavelength dependence (725-1025 nm) of the threshold for nanosecond optical breakdown in water revealed steps consistent with breakdown initiation by multiphoton ionization, with an initiation energy of about 6.6 eV. This value is considerably smaller than the autoionization threshold of about 9.5 eV, which can be regarded as band gap relevant for avalanche ionization. Breakdown initiation is likely to occur via excitation of a valence band electron into a solvated state, followed by rapid excitation into the conduction band. Theoretical analysis based on these assumptions suggests that the seed electron density required for initiating avalanche ionization amounts to 2.5 ×1015c m-3 at 725 nm and drops to 1.1 ×1012c m-3 at 1025 nm. These results demand changes of future breakdown modeling for water, including the use of a larger band gap than previously employed, the introduction of an intermediate energy level for initiation, and consideration of the wavelength dependence of seed electron density.

Internal standards for use in the comprehensive analysis of polychlorinated aromatic hydrocarbons using gas chromatography combined with multiphoton ionization mass spectrometry.

PubMed

Li, Adan; Imasaka, Totaro

2016-10-28

To decrease health-risks to humans, non-toxic compounds were evaluated for use as internal standards for calibrating data obtained by gas chromatography/multiphoton ionization mass spectrometry (GC-MPI-MS) using an ultraviolet femtosecond laser as the ionization source. The retention time in the mass chromatogram was calibrated using a retention index, in which a series of n-alkanes was employed as internal standards for evaluating the retention times for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs). To compensate for changes in signal intensity in MPI-MS, the dependence of signal intensity on the laser pulse energy was investigated for the dioxin-like compounds, in addition to five non-toxic aromatic hydrocarbons, that were used as internal standards. Based on their similar behavior,the non-toxic PCDD/PCDF, its 13 C-isotope, and pentachlorobenzene behave similarly, we conclude that they can be used for calibrating the signal intensities in MPI-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

Kα resonance fluorescence in Al, Ti, Cu and potential applications for X-ray sources

NASA Astrophysics Data System (ADS)

Nahar, Sultana N.; Pradhan, Anil K.

2015-04-01

The Kα resonance fluorescence (RFL) effect via photoabsorptions of inner shell electrons as the element goes through multiple ionization states is studied. We demonstrate that the resonances observed recently in Kα (1s-2p) fluorescence in aluminum plasmas by using a high-intensity X-ray free-electron laser [1] are basically K-shell resonances in hollow atoms going through multiple ionization states at resonant energies as predicted earlier for gold and iron ions [2]. These resonances are formed below the K-shell ionization edge and shift toward higher energies with ionization states, as observed. Fluorescence emission intensities depend on transition probabilities for each ionization stage of the given element for all possible Kα (1 s → 2 p) transition arrays. The present calculations for resonant photoabsorptions of Kα photons in Al have reproduced experimentally observed features. Resonant cross sections and absorption coefficients are presented for possible observation of Kα RFL in the resonant energy ranges of 4.5-5.0 keV for Ti ions and 8.0-8.7 keV for Cu ions respectively. We suggest that theoretically the Kα RFL process may be driven to enhance the Auger cycle by a twin-beam monochromatic X-ray source, tuned to the K-edge and Kα energies, with potential applications such as the development of narrow-band biomedical X-ray devices.

Real-time analysis of organic compounds in ship engine aerosol emissions using resonance-enhanced multiphoton ionisation and proton transfer mass spectrometry.

PubMed

Radischat, Christian; Sippula, Olli; Stengel, Benjamin; Klingbeil, Sophie; Sklorz, Martin; Rabe, Rom; Streibel, Thorsten; Harndorf, Horst; Zimmermann, Ralf

2015-08-01

Organic combustion aerosols from a marine medium-speed diesel engine, capable to run on distillate (diesel fuel) and residual fuels (heavy fuel oil), were investigated under various operating conditions and engine parameters. The online chemical characterisation of the organic components was conducted using a resonance-enhanced multiphoton ionisation time-of-flight mass spectrometer (REMPI TOF MS) and a proton transfer reaction-quadrupole mass spectrometer (PTR-QMS). Oxygenated species, alkenes and aromatic hydrocarbons were characterised. Especially the aromatic hydrocarbons and their alkylated derivatives were very prominent in the exhaust of both fuels. Emission factors of known health-hazardous compounds (e.g. mono- and poly-aromatic hydrocarbons) were calculated and found in higher amounts for heavy fuel oil (HFO) at typical engine loadings. Lower engine loads lead in general to increasing emissions for both fuels for almost every compound, e.g. naphthalene emissions varied for diesel fuel exhaust between 0.7 mg/kWh (75 % engine load, late start of injection (SOI)) and 11.8 mg/kWh (10 % engine load, late SOI) and for HFO exhaust between 3.3 and 60.5 mg/kWh, respectively. Both used mass spectrometric techniques showed that they are particularly suitable methods for online monitoring of combustion compounds and very helpful for the characterisation of health-relevant substances. Graphical abstract Three-dimensional REMPI data of organic species in diesel fuel and heavy fuel oil exhaust.

A simple resonance enhanced laser ionization scheme for CO via the A1Π state

NASA Astrophysics Data System (ADS)

Sun, Z. F.; von Zastrow, A. D.; Parker, D. H.

2017-07-01

We investigate the laser ionization process taking place when the CO molecule is exposed to vacuum ultraviolet (VUV) radiation resonant with the CO A1Π (v = 0) ← X1Σ+ (v = 0) transition around 154 nm, along with the ultraviolet (UV) and visible (Red) radiation used to generate VUV by four-wave difference-frequency mixing. By measuring the CO+ ion recoil and a room temperature gas spectrum, it is possible to assign the ionization process as 1 + 1' + 1'' REMPI where the one-photon steps refer to the VUV, UV, and Red radiation, respectively. Resonance enhanced ionization of rotational states around J = 12 arise due to the overlap of the fixed wavelength UV (˜250 nm) with the R band-head of a transition assigned to CO E1Π (v = 6) ← A1Π (v = 0) with a term value of 104 787.5 cm-1. The REMPI process is efficient and polarization sensitive and should be useful in a wide range of studies involving nascent CO.

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation

NASA Astrophysics Data System (ADS)

Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E.; Thiré, Nicolas; Fowe, Emmanuel P.; Bisson, Éric; Hebeisen, Christoph T.; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D.; Sanderson, Joseph; Schuurman, Michael S.; Légaré, François

2014-07-01

The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations.

Investigation of the RbCa molecule: Experiment and theory.

PubMed

Pototschnig, Johann V; Krois, Günter; Lackner, Florian; Ernst, Wolfgang E

2015-04-01

We present a thorough theoretical and experimental study of the electronic structure of RbCa. The mixed alkali-alkaline earth molecule RbCa was formed on superfluid helium nanodroplets. Excited states of the molecule in the range of 13 000-23 000 cm -1 were recorded by resonance enhanced multi-photon ionization time-of-flight spectroscopy. The experiment is accompanied by high level ab initio calculations of ground and excited state properties, utilizing a multireference configuration interaction method based on multiconfigurational self consistent field calculations. With this approach the potential energy curves and permanent electric dipole moments of 24 electronic states were calculated. In addition we computed the transition dipole moments for transitions from the ground into excited states. The combination of experiment and theory allowed the assignment of features in the recorded spectrum to the excited [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] states, where the experiment allowed to benchmark the calculation. This is the first experimental work giving insight into the previously unknown RbCa molecule, which offers great prospects in ultracold molecular physics due to its magnetic and electronic dipole moment in the [Formula: see text] ground state.

Velocity-tunable slow beams of cold O2 in a single spin-rovibronic state with full angular-momentum orientation by multistage Zeeman deceleration

NASA Astrophysics Data System (ADS)

Wiederkehr, A. W.; Schmutz, H.; Motsch, M.; Merkt, F.

2012-08-01

Cold samples of oxygen molecules in supersonic beams have been decelerated from initial velocities of 390 and 450 m s-1 to final velocities in the range between 150 and 280 m s-1 using a 90-stage Zeeman decelerator. (2 + 1) resonance-enhanced-multiphoton-ionization (REMPI) spectra of the 3sσ g 3Π g (C) ? two-photon transition of O2 have been recorded to characterize the state selectivity of the deceleration process. The decelerated molecular sample was found to consist exclusively of molecules in the J ‧‧ = 2 spin-rotational component of the X ? ground state of O2. Measurements of the REMPI spectra using linearly polarized laser radiation with polarization vector parallel to the decelerator axis, and thus to the magnetic-field vector of the deceleration solenoids, further showed that only the ? magnetic sublevel of the N‧‧ = 1, J ‧‧ = 2 spin-rotational level is populated in the decelerated sample, which therefore is characterized by a fully oriented total-angular-momentum vector. By maintaining a weak quantization magnetic field beyond the decelerator, the polarization of the sample could be maintained over the 5 cm distance separating the last deceleration solenoid and the detection region.

Real-time monitoring of BTEX in air via ambient-pressure MPI

NASA Astrophysics Data System (ADS)

Swenson, Orven F.; Carriere, Josef P.; Isensee, Harlan; Gillispie, Gregory D.; Cooper, William F.; Dvorak, Michael A.

1998-05-01

We have developed and begun to field test a very sensitive method for real-time measurements of single-ring aromatic hydrocarbons in ambient air. In this study, we focus on the efficient 1 + 1 resonance enhanced multiphoton ionization (REMPI) of the BTEX species in the narrow region between 266 and 267 nm. We particularly emphasize 266.7 nm, a wavelength at which both benzene and toluene exhibit a sharp absorbance feature and benzene and its alkylated derivatives all absorb. An optical parametric oscillator system generating 266.7 nm, a REMPI cell, and digital oscilloscope detector are mounted on a breadboard attached to a small cart. In the first field test, the cart was wheeled through the various rooms of a chemistry research complex. Leakage of fuel through the gas caps of cars and light trucks in a parking lot was the subject of the second field test. The same apparatus was also used for a study in which the performance of the REMPI detector and a conventional photoionization detector were compared as a BTEX mixture was eluted by gas chromatography. Among the potential applications of the methodology are on-site analysis of combustion and manufacturing processes, soil gas and water headspace monitoring, space cabin and building air quality, and fuel leak detection.

Gas-phase spectroscopy of synephrine by laser desorption supersonic jet technique.

PubMed

Ishiuchi, Shun-ichi; Asakawa, Toshiro; Mitsuda, Haruhiko; Miyazaki, Mitsuhiko; Chakraborty, Shamik; Fujii, Masaaki

2011-09-22

In our previous work, we found that synephrine has six conformers in the gas phase, while adrenaline, which is a catecholamine and has the same side chain as synephrine, has been reported to have only two conformers. To determine the conformational geometries of synephrine, we measured resonance enhanced multiphoton ionization, ultraviolet-ultraviolet hole burning, and infrared dip spectra by utilizing the laser desorption supersonic jet technique. By comparing the observed infrared spectra with theoretical ones, we assigned geometries except for the orientations of the phenolic OH group. Comparison between the determined structures of synephrine and those of 2-methylaminno-1-phenylethanol, which has the same side chain as synephrine but no phenol OH group, leads to the conclusion that the phenolic OH group in synephrine does not affect the conformational flexibility of the side chain. In the case of adrenaline, which is expected to have 12 conformers if there are no interactions between the catecholic OH groups and the side chain, some interactions possibly exist between them because only two conformations are observed. By estimation of the dipole-dipole interaction energy between partial dipole moments of the catecholic OH groups and the side chain, it was concluded that the dipole-dipole interaction stabilizes specific conformers which are actually observed. © 2011 American Chemical Society

Plasma effect on fast-electron-impact-ionization from 2p state of hydrogen-like ions

NASA Astrophysics Data System (ADS)

Qi, Y. Y.; Ning, L. N.; Wang, J. G.; Qu, Y. Z.

2013-12-01

Plasma effects on the high-energy electron-impact ionization process from 2p orbital of Hydrogen-like ions embedded in weakly coupled plasmas are investigated in the first Born approximation. The plasma screening of the Coulomb interaction between charged particles is represented by the Debye Hückel model. The screening of Coulomb interactions decreases the ionization energies and varies the wave functions for not only the bound orbital but also the continuum; the number of the summation for the angular-momentum states in the generalized oscillator strength densities is reduced with the plasma screening stronger when the ratio of ɛ /I2p (I2p is the ionization energy of 2p state and ɛ is the energy of the continuum electron) is kept, and then the contribution from the lower-angular-momentum states dominates the generalized oscillator strength densities, so the threshold phenomenon in the generalized oscillator strength densities and the double differential cross sections are remarkable: The accessional minima, the outstanding enhancement, and the resonance peaks emerge a certain energy region, whose energy position and width are related to the vicinity between δ and the critical value δnlc, corresponding to the special plasma condition when the bound state |nl⟩ just enters the continuum; the multiple virtual-state enhancement and the multiple shape resonances in a certain energy domain also appear in the single differential cross section whenever the plasma screening parameter passes through a critical value δnlc, which is similar to the photo-ionization process but different from it, where the dipole transition only happens, but multi-pole transition will occur in the electron-impact ionization process, so its multiple virtual-state enhancements and the multiple shape resonances appear more frequently than the photo-ionization process.

Resonant Pump-dump Quantum Control of Solvated Dye Molecules with Phase Jumps

NASA Astrophysics Data System (ADS)

Konar, Arkaprabha; Lozovoy, Vadim; Dantus, Marcos

2014-03-01

Quantum coherent control of two photon and multiphoton excitation processes in atomic and condensed phase systems employing phase jumps has been well studied and understood. Here we demonstrate coherent quantum control of a two photon resonant pump-dump process in a complex solvated dye molecule. Phase jump in the frequency domain via a pulse shaper is employed to coherently enhance the stimulated emission by an order of magnitude when compared to transform limited pulses. Red shifted stimulated emission from successive low energy Stokes shifted excited states leading to narrowband emission are observed upon scanning the pi step across the excitation spectrum. A binary search space routine was also employed to investigate the effects of other types of phase jumps on stimulated emission and to determine the optimum phase that maximizes the emission. Understanding the underlying mechanism of this kind of enhancement will guide us in designing pulse shapes for enhancing stimulated emission, which can be further applied in the field of imaging.

Observations of magnetospheric ionization enhancements using upper-hybrid resonance noise band data from the RAE-1 satellite

NASA Technical Reports Server (NTRS)

Mosier, S. R.

1975-01-01

Noise bands associated with the upper-hybrid resonance were used to provide direct evidence for the existence of regions of enhanced density in the equatorial magnetosphere near L = 2. Density enhancements ranging from several percent to as high as 45 percent are observed with radial dimensions of several hundred kilometers. The enhancement characteristics strongly suggest their identification as magnetospheric whistler ducts.

Tabletop Imaging of Structural Evolutions in Chemical Reactions

NASA Astrophysics Data System (ADS)

Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E.; Thiré, Nicolas; Fowe, Emmanuel P.; Bisson, Éric; Hebeisen, Christoph T.; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D.; Sanderson, Joseph; Schuurman, Michael S.; Légaré, François

The first high-resolution molecular movie of proton migration in the acetylene cation is obtained using a tabletop multiphoton pump-probe approach—an alternative to demanding free-electron-lasers and other VUV light sources when ionizing from the HOMO-1.

Experimental observation of multiphoton Thomson scattering

NASA Astrophysics Data System (ADS)

Yan, Wenchao; Golovin, Grigory; Fruhling, Colton; Haden, Daniel; Zhang, Ping; Zhang, Jun; Zhao, Baozhen; Liu, Cheng; Chen, Shouyuan; Banerjee, Sudeep; Umstadter, Donald

2016-10-01

With the advent of high-power lasers, several multiphoton processes have been reported involving electrons in strong fields. For electrons that were initially bound to atoms, both multiphoton ionization and scattering have been reported. However, for free electrons, only low-order harmonic generation has been observed until now. This limitation stems from past difficulty in achieving the required ultra-high-field strengths in scattering experiments. Highly relativistic laser intensities are required to reach the multiphoton regime of Thomson scattering, and generate high harmonics from free electrons. The scaling parameter is the normalized vector potential (a0). Previous experiments have observed phenomena in the weakly relativistic case (a0 >> 1). In ultra-intense fields (a0 >>1), the anomalous electron trajectory is predicted to produce a spectrum characterized by the merging of multiple high-order harmonic generation into a continuum. This may be viewed as the multiphoton Thomson scattering regime analogous to the wiggler of a synchrotron. Thus, the light produced reflects the electrons behavior in an ultra-intense lase field. We discuss the first experiments in the highly relativistic case (a0 15). This material is based upon work supported by NSF No. PHY-153700; US DOE, Office of Science, BES, # DE-FG02-05ER15663; AFOSR # FA9550-11-1-0157; and DHS DNDO # HSHQDC-13-C-B0036.

Surface-plasmon resonance-enhanced multiphoton emission of high-brightness electron beams from a nanostructured copper cathode.

PubMed

Li, R K; To, H; Andonian, G; Feng, J; Polyakov, A; Scoby, C M; Thompson, K; Wan, W; Padmore, H A; Musumeci, P

2013-02-15

We experimentally investigate surface-plasmon assisted photoemission to enhance the efficiency of metallic photocathodes for high-brightness electron sources. A nanohole array-based copper surface was designed to exhibit a plasmonic response at 800 nm, fabricated using the focused ion beam milling technique, optically characterized and tested as a photocathode in a high power radio frequency photoinjector. Because of the larger absorption and localization of the optical field intensity, the charge yield observed under ultrashort laser pulse illumination is increased by more than 100 times compared to a flat surface. We also present the first beam characterization results (intrinsic emittance and bunch length) from a nanostructured photocathode.

Multiple product pathways in photodissociation of nitromethane at 213 nm

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

Sumida, Masataka; Kohge, Yasunori; Yamasaki, Katsuyoshi

2016-02-14

In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π{sup *} transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH{sub 3}, NO(X {sup 2}Π, A {sup 2}Σ{sup +}), and O({sup 3}P{sub J}) photofragments. The rotationally state-resolved scattering distribution of the CH{sub 3} fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH{sub 3} fragment indicated the production of themore » NO{sub 2} counter-product in the electronic excited state, wherein 1 {sup 2}B{sub 2} was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O({sup 3}P{sub J}) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A {sup 2}Σ{sup +}) fragment, which was detected by ionization spectroscopy via the Rydberg ←A {sup 2}Σ{sup +} transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH{sub 3} + NO{sub 2},CH{sub 3} + NO + O,CH{sub 3}O + NO, and CH{sub 3}NO + O, following the π → π{sup *} transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.« less

Weak-field multiphoton femtosecond coherent control in the single-cycle regime.

PubMed

Chuntonov, Lev; Fleischer, Avner; Amitay, Zohar

2011-03-28

Weak-field coherent phase control of atomic non-resonant multiphoton excitation induced by shaped femtosecond pulses is studied theoretically in the single-cycle regime. The carrier-envelope phase (CEP) of the pulse, which in the multi-cycle regime does not play any control role, is shown here to be a new effective control parameter that its effect is highly sensitive to the spectral position of the ultrabroad spectrum. Rationally chosen position of the ultrabroadband spectrum coherently induces several groups of multiphoton transitions from the ground state to the excited state of the system: transitions involving only absorbed photons as well as Raman transitions involving both absorbed and emitted photons. The intra-group interference is controlled by the relative spectral phase of the different frequency components of the pulse, while the inter-group interference is controlled jointly by the CEP and the relative spectral phase. Specifically, non-resonant two- and three-photon excitation is studied in a simple model system within the perturbative frequency-domain framework. The developed intuition is then applied to weak-field multiphoton excitation of atomic cesium (Cs), where the simplified model is verified by non-perturbative numerical solution of the time-dependent Schrödinger equation. We expect this work to serve as a basis for a new line of femtosecond coherent control experiments.

Spectroscopy of Isolated Prebiotic Nucleobases

NASA Technical Reports Server (NTRS)

Svadlenak, Nathan; Callahan, Michael P.; Ligare, Marshall; Gulian, Lisa; Gengeliczki, Zsolt; Nachtigallova, Dana; Hobza, Pavel; deVries, Mattanjah

2011-01-01

We use multiphoton ionization and double resonance spectroscopy to study the excited state dynamics of biologically relevant molecules as well as prebiotic nucleobases, isolated in the gas phase. Molecules that are biologically relevant to life today tend to exhibit short excited state lifetimes compared to similar but non-biologically relevant analogs. The mechanism is internal conversion, which may help protect the biologically active molecules from UV damage. This process is governed by conical intersections that depend very strongly on molecular structure. Therefore we have studied purines and pyrimidines with systematic variations of structure, including substitutions, tautomeric forms, and cluster structures that represent different base pair binding motifs. These structural variations also include possible alternate base pairs that may shed light on prebiotic chemistry. With this in mind we have begun to probe the ultrafast dynamics of molecules that exhibit very short excited states and search for evidence of internal conversions.

Exploration of laser-driven electron-multirescattering dynamics in high-order harmonic generation

DOE PAGES

Li, Peng -Cheng; Sheu, Yae -Lin; Jooya, Hossein Z.; ...

2016-09-06

Multiple rescattering processes play an important role in high-order harmonic generation (HHG) in an intense laser field. However, the underlying multi-rescattering dynamics are still largely unexplored. Here we investigate the dynamical origin of multiple rescattering processes in HHG associated with the odd and even number of returning times of the electron to the parent ion. We perform fully ab initio quantum calculations and extend the empirical mode decomposition method to extract the individual multiple scattering contributions in HHG. We find that the tunneling ionization regime is responsible for the odd number times of rescattering and the corresponding short trajectories aremore » dominant. On the other hand, the multiphoton ionization regime is responsible for the even number times of rescattering and the corresponding long trajectories are dominant. Moreover, we discover that the multiphoton- and tunneling-ionization regimes in multiple rescattering processes occur alternatively. Our results uncover the dynamical origin of multiple rescattering processes in HHG for the first time. As a result, it also provides new insight regarding the control of the multiple rescattering processes for the optimal generation of ultrabroad band supercontinuum spectra and the production of single ultrashort attosecond laser pulse.« less

Exploration of laser-driven electron-multirescattering dynamics in high-order harmonic generation

PubMed Central

Li, Peng-Cheng; Sheu, Yae-Lin; Jooya, Hossein Z.; Zhou, Xiao-Xin; Chu, Shih-I

2016-01-01

Multiple rescattering processes play an important role in high-order harmonic generation (HHG) in an intense laser field. However, the underlying multi-rescattering dynamics are still largely unexplored. Here we investigate the dynamical origin of multiple rescattering processes in HHG associated with the odd and even number of returning times of the electron to the parent ion. We perform fully ab initio quantum calculations and extend the empirical mode decomposition method to extract the individual multiple scattering contributions in HHG. We find that the tunneling ionization regime is responsible for the odd number times of rescattering and the corresponding short trajectories are dominant. On the other hand, the multiphoton ionization regime is responsible for the even number times of rescattering and the corresponding long trajectories are dominant. Moreover, we discover that the multiphoton- and tunneling-ionization regimes in multiple rescattering processes occur alternatively. Our results uncover the dynamical origin of multiple rescattering processes in HHG for the first time. It also provides new insight regarding the control of the multiple rescattering processes for the optimal generation of ultrabroad band supercontinuum spectra and the production of single ultrashort attosecond laser pulse. PMID:27596056

Exploration of laser-driven electron-multirescattering dynamics in high-order harmonic generation.

PubMed

Li, Peng-Cheng; Sheu, Yae-Lin; Jooya, Hossein Z; Zhou, Xiao-Xin; Chu, Shih-I

2016-09-06

Multiple rescattering processes play an important role in high-order harmonic generation (HHG) in an intense laser field. However, the underlying multi-rescattering dynamics are still largely unexplored. Here we investigate the dynamical origin of multiple rescattering processes in HHG associated with the odd and even number of returning times of the electron to the parent ion. We perform fully ab initio quantum calculations and extend the empirical mode decomposition method to extract the individual multiple scattering contributions in HHG. We find that the tunneling ionization regime is responsible for the odd number times of rescattering and the corresponding short trajectories are dominant. On the other hand, the multiphoton ionization regime is responsible for the even number times of rescattering and the corresponding long trajectories are dominant. Moreover, we discover that the multiphoton- and tunneling-ionization regimes in multiple rescattering processes occur alternatively. Our results uncover the dynamical origin of multiple rescattering processes in HHG for the first time. It also provides new insight regarding the control of the multiple rescattering processes for the optimal generation of ultrabroad band supercontinuum spectra and the production of single ultrashort attosecond laser pulse.

Bond-selective photodissociation of partially deuterated ammonia molecules: Photodissociations of vibrationally excited NHD2 in the 5νNH state and NH2D in the 5νND state

NASA Astrophysics Data System (ADS)

Akagi, Hiroshi; Yokoyama, Keiichi; Yokoyama, Atsushi

2004-03-01

Ultraviolet photodissociation of NHD2 excited to the fourth overtone state of the NH stretching mode (5νNH) and NH2D excited to that of the ND stretching mode (5νND) has been investigated by using a crossed laser and molecular beams method. Branching ratio between the NH and ND bond dissociations has been determined by utilizing a (2+1) resonance enhanced multiphoton ionization scheme of H and D atoms. For the photolysis of NHD2 in the 5νNH state, the NH dissociation cross section is 5.1±1.4 times as large as the ND dissociation cross section per bond. On the other hand, for the photolysis of NH2D in the 5νND state, the ratio of the NH dissociation cross section per bond to the ND dissociation cross section decreases to 0.68±0.16. In comparison with the branching ratios for the photolysis of vibrationally unexcited NH2D and NHD2 [Koda and Back, Can. J. Chem. 55, 1380 (1977)], the present results indicate that the excitation of the NH stretching mode enhances the NH dissociation with ca. two times larger NH/ND branching ratio, whereas the excitation of the ND stretching mode results in the preferential ND dissociation with ca. 3-4 times larger ND/NH branching ratio than that for the vibrational ground states. The mechanism of the bond-selective enhancement has been discussed in terms of the energetics and dynamics of wave packet.

Reassigning the CaH+ 11Σ → 21Σ vibronic transition with CaD+

NASA Astrophysics Data System (ADS)

Condoluci, J.; Janardan, S.; Calvin, A. T.; Rugango, R.; Shu, G.; Sherrill, C. D.; Brown, K. R.

2017-12-01

We observe vibronic transitions in CaD+ between the 11Σ and 21Σ electronic states by resonance enhanced multiphoton photodissociation spectroscopy in a Coulomb crystal. The vibronic transitions are compared with previous measurements on CaH+. The result is a revised assignment of the CaH+ vibronic levels and a disagreement with multi-state-complete-active-space second-order perturbation theory theoretical calculations by approximately 700 cm-1. Updated high-level coupled-cluster calculations that include core-valence correlations reduce the disagreement between theory and experiment to 300 cm-1.

Production of cold beams of ND{sub 3} with variable rotational state distributions by electrostatic extraction of He and Ne buffer-gas-cooled beams

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

Twyman, Kathryn S.; Bell, Martin T.; Heazlewood, Brianna R.

2014-07-14

The measurement of the rotational state distribution of a velocity-selected, buffer-gas-cooled beam of ND{sub 3} is described. In an apparatus recently constructed to study cold ion-molecule collisions, the ND{sub 3} beam is extracted from a cryogenically cooled buffer-gas cell using a 2.15 m long electrostatic quadrupole guide with three 90° bends. (2+1) resonance enhanced multiphoton ionization spectra of molecules exiting the guide show that beams of ND{sub 3} can be produced with rotational state populations corresponding to approximately T{sub rot} = 9–18 K, achieved through manipulation of the temperature of the buffer-gas cell (operated at 6 K or 17 K),more » the identity of the buffer gas (He or Ne), or the relative densities of the buffer gas and ND{sub 3}. The translational temperature of the guided ND{sub 3} is found to be similar in a 6 K helium and 17 K neon buffer-gas cell (peak kinetic energies of 6.92(0.13) K and 5.90(0.01) K, respectively). The characterization of this cold-molecule source provides an opportunity for the first experimental investigations into the rotational dependence of reaction cross sections in low temperature collisions.« less

Spectroscopy of Cold LiCa Molecules Formed on Helium Nanodroplets

PubMed Central

2013-01-01

We report on the formation of mixed alkali–alkaline earth molecules (LiCa) on helium nanodroplets and present a comprehensive experimental and theoretical study of the ground and excited states of LiCa. Resonance enhanced multiphoton ionization time-of-flight (REMPI-TOF) spectroscopy and laser induced fluorescence (LIF) spectroscopy were used for the experimental investigation of LiCa from 15000 to 25500 cm–1. The 42Σ+ and 32Π states show a vibrational structure accompanied by distinct phonon wings, which allows us to determine molecular parameters as well as to study the interaction of the molecule with the helium droplet. Higher excited states (42Π, 52Σ+, 52Π, and 62Σ+) are not vibrationally resolved and vibronic transitions start to overlap. The experimental spectrum is well reproduced by high-level ab initio calculations. By using a multireference configuration interaction (MRCI) approach, we calculated the 19 lowest lying potential energy curves (PECs) of the LiCa molecule. On the basis of these calculations, we could identify previously unobserved transitions. Our results demonstrate that the helium droplet isolation approach is a powerful method for the characterization of tailor-made alkali–alkaline earth molecules. In this way, important contributions can be made to the search for optimal pathways toward the creation of ultracold alkali–alkaline earth ground state molecules from the corresponding atomic species. Furthermore, a test for PECs calculated by ab initio methods is provided. PMID:24028555

Advanced Laser Architecture for Two-Step Laser Tandem Mass Spectrometer

NASA Technical Reports Server (NTRS)

Fahey, Molly E.; Li, Steven X.; Yu, Anthony W.; Getty, Stephanie A.

2016-01-01

Future astrobiology missions will focus on planets with significant astrochemical or potential astrobiological features, such as small, primitive bodies and the icy moons of the outer planets that may host diverse organic compounds. These missions require advanced instrument techniques to fully and unambiguously characterize the composition of surface and dust materials. Laser desorptionionization mass spectrometry (LDMS) is an emerging instrument technology for in situ mass analysis of non-volatile sample composition. A recent Goddard LDMS advancement is the two-step laser tandem mass spectrometer (L2MS) instrument to address the need for future flight instrumentation to deconvolve complex organic signatures. The L2MS prototype uses a resonance enhanced multi-photon laser ionization mechanism to selectively detect aromatic species from a more complex sample. By neglecting the aliphatic and inorganic mineral signatures in the two-step mass spectrum, the L2MS approach can provide both mass assignments and clues to structural information for an in situ investigation of non-volatile sample composition. In this paper we will describe our development effort on a new laser architecture that is based on the previously flown Lunar Orbiter Laser Altimeter (LOLA) laser transmitter for the L2MS instrument. The laser provides two discrete midinfrared wavelengths (2.8 m and 3.4 m) using monolithic optical parametric oscillators and ultraviolet (UV) wavelength (266 nm) on a single laser bench with a straightforward development path toward flight readiness.

Near-real-time combustion monitoring for PCDD/PCDF indicators by GC-REMPI-TOFMS.

PubMed

Gullett, Brian K; Oudejans, Lukas; Tabor, Dennis; Touati, Abderrahmane; Ryan, Shawn

2012-01-17

The boiler exit flue gas of a municipal waste combustor was sampled to evaluate an online monitoring system for chlorobenzene congeners as indicators of polychlorinated dibenzodioxin and dibenzofuran (PCDD/PCDF) concentrations. Continuous measurements of chlorobenzene congeners using gas chromatography coupled to a resonance-enhanced multiphoton ionization - time-of-flight mass spectrometry (GC-REMPI-TOFMS) system were compared over 5-min periods with conventional sampling methods for PCDD/PCDF. Three pairs of values were taken every hour over a period of three days to characterize the combustor's response to transient operating conditions (shutdowns and startups). Isolation of specific chlorobenzene congeners from other same-mass compounds was accomplished by using a GC column separator ahead of the REMPI-TOFMS. The 50-fold variation of PCDD/PCDF concentration was paralleled by similar changes in monitored compounds of 1,4-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4,5-tetrachlorobenzene. A correlation of R = 0.85 and 0.89 was established between 40 pairs of simultaneous 5-min GC-REMPI-TOFMS measurements of 1,2,4-trichlorobenzene and 5 min conventional sampling and analysis for the TEQ and Total measures of PCDD/PCDF, respectively. The GC-REMPI-TOFMS system can be used to provide frequent measures of correlative PCDD/PCDF concentration thereby allowing for an understanding of measures to minimize PCDD/PCDF formation and develop operational feedback to limit emissions.

Consistent Assignment of the Vibrations of Monohalosubstituted Benzenes

NASA Astrophysics Data System (ADS)

Harris, Joe; Andrejeva, Anna; Tuttle, William Duncan; Pugliesi, Igor; Schriever, Christian; Wright, Tim

2014-06-01

When substituted benzenes become a focus of a spectroscopic study there are various well known vibrational labelling schemes present, however it was shown in recent works the description of monohalobenzene vibrations in terms of benzene modes (ie. Wilson notation) is questionable in some cases. A new scheme is presented which uses the motions of monofluorobenzene vibrations as a basis for labelling vibrational assignments of monosubstituted benzenes.d The scheme has been successfully applied to the ground and excited states of toluene and its deuterated-methyl group isotopologue. Here we present the application of the scheme to fluorobenzene and its fully deuterated analogue. One-colour resonance-enhanced multiphoton ionization (REMPI) spectroscopy was employed in order to characterise the fluorobenzene and fluorobenzene-d5 excited state. E. B. Wilson Jr., Phys. Rev., 45, 706 (1934) G .Varsanyi, Assignments of the Vibrational Spectra of Seven Hundred Benzene Derivatives,Wiley, New York, 1974, Vol. I and II I. Pugliesi, N. C. Tonge and M. C. R. Cockett, J. Chem. Phys., 129, 104303 (2008) A. M. Gardner and T. G. Wright, J. Chem. Phys., 135,114305 (2011) A. M. Gardner, A. M. Green, V. M. Tame-Reyes, V. H. K. Wilton and T. G. Wright, 138, 134303 (2013) A. M. Gardner, A. M. Green, V. M. Tame-Reyes, K. L. Reid, J. A. Davies, V. H. K. Wilton and T. G. Wright, manuscript accepted

Photodissociation dynamics of propanal and isobutanal: The Norrish Type I pathway

NASA Astrophysics Data System (ADS)

Harrison, Aaron W.; Kable, Scott H.

2018-04-01

The Norrish Type I photodissociation of two aliphatic aldehydes, propanal and isobutanal, has been investigated using velocity-map imaging. The HCO photoproduct of this reaction was probed using a 1+1 resonance-enhanced multiphoton ionization scheme via the 3p2Π Rydberg state. The velocity map images of HCO+ were collected across a range of photolysis energies for both species from 30 500 to 33 000 cm-1 (λ = 312-327 nm). The corresponding translational energy distributions show that the majority of the available energy goes into the translational motion of the products (55%-68%) with this fraction increasing as the T1 barrier is approached. Analysis of the translational energy distributions was also used to determine the aldehyde α C-C bond dissociation energies which were found to be 339.8 ± 2.5 and 331.2 ± 2.5 kJ/mol for propanal and isobutanal, respectively. These values were also found to be in good agreement with the computed dissociation energies using G4 and CCSD(T)/aug-cc-pVTZ//M062X/aug-cc-pVTZ levels of theory. Furthermore, these dissociation energies, combined with the known ΔfH (0 K) of the reaction products, provided the ΔfH (0 K) of propanal and isobutanal which were calculated to be -167.3 ± 2.5 and -184.0 ± 2.5 kJ/mol, respectively.

Application of modern online instrumentation for chemical analysis of gas and particulate phases of exhaust at the European Commission heavy-duty vehicle emission laboratory.

PubMed

Adam, T W; Chirico, R; Clairotte, M; Elsasser, M; Manfredi, U; Martini, G; Sklorz, M; Streibel, T; Heringa, M F; Decarlo, P F; Baltensperger, U; De Santi, G; Krasenbrink, A; Zimmermann, R; Prevot, A S H; Astorga, C

2011-01-01

The European Commission recently established a novel test facility for heavy-duty vehicles to enhance more sustainable transport. The facility enables the study of energy efficiency of various fuels/scenarios as well as the chemical composition of evolved exhaust emissions. Sophisticated instrumentation for real-time analysis of the gas and particulate phases of exhaust has been implemented. Thereby, gas-phase characterization was carried out by a Fourier transform infrared spectrometer (FT-IR; carbonyls, nitrogen-containing species, small hydrocarbons) and a resonance-enhanced multiphoton ionization time-of-flight mass spectrometer (REMPI-TOFMS; monocyclic and polycyclic aromatic hydrocarbons). For analysis of the particulate phase, a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS; organic matter, chloride, nitrate), a condensation particle counter (CPC; particle number), and a multiangle absorption photometer (MAAP; black carbon) were applied. In this paper, the first application of the new facility in combination with the described instruments is presented, whereby a medium-size truck was investigated by applying different driving cycles. The goal was simultaneous chemical characterization of a great variety of gaseous compounds and particulate matter in exhaust on a real-time basis. The time-resolved data allowed new approaches to view the results; for example, emission factors were normalized to time-resolved consumption of fuel and were related to emission factors evolved during high speeds. Compounds could be identified that followed the fuel consumption, others showed very different behavior. In particular, engine cold start, engine ignition (unburned fuel), and high-speed events resulted in unique emission patterns.

Study on the decomposition of trace benzene over V2O5-WO3 ...

EPA Pesticide Factsheets

Commercial and laboratory-prepared V2O5–WO3/TiO2-based catalysts with different compositions were tested for catalytic decomposition of chlorobenzene （ClBz） in simulated flue gas. Resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) was employed to measure real-time, trace concentrations of ClBz contained in the flue gas before and after the catalyst. The effects of various parameters, including vanadium content of the catalyst, the catalyst support, as well as the reaction temperature on decomposition of ClBz were investigated. The results showed that the ClBz decomposition efficiency was significantly enhanced when nano-TiO2 instead of conventional TiO2 was used as the catalyst support. No promotion effects were found in the ClBz decomposition process when the catalysts were wet-impregnated with CuO and CeO2. Tests with different concentrations (1,000, 500, and 100 ppb) of ClBz showed that ClBz-decomposition efficiency decreased with increasing concentration, unless active sites were plentiful. A comparison between ClBz and benzene decomposition on the V2O5–WO3/TiO2-based catalyst and the relative kinetics analysis showed that two different active sites were likely involved in the decomposition mechanism and the V=O and V-O-Ti groups may only work for the degradation of the phenyl group and the benzene ring rather than the C-Cl bond. V2O5-WO3/TiO2 based catalysts, that have been used for destruction of a wide variet

Video-rate resonant scanning multiphoton microscopy

PubMed Central

Kirkpatrick, Nathaniel D.; Chung, Euiheon; Cook, Daniel C.; Han, Xiaoxing; Gruionu, Gabriel; Liao, Shan; Munn, Lance L.; Padera, Timothy P.; Fukumura, Dai; Jain, Rakesh K.

2013-01-01

The abnormal tumor microenvironment fuels tumor progression, metastasis, immune suppression, and treatment resistance. Over last several decades, developments in and applications of intravital microscopy have provided unprecedented insights into the dynamics of the tumor microenvironment. In particular, intravital multiphoton microscopy has revealed the abnormal structure and function of tumor-associated blood and lymphatic vessels, the role of aberrant tumor matrix in drug delivery, invasion and metastasis of tumor cells, the dynamics of immune cell trafficking to and within tumors, and gene expression in tumors. However, traditional multiphoton microscopy suffers from inherently slow imaging rates—only a few frames per second, thus unable to capture more rapid events such as blood flow, lymphatic flow, and cell movement within vessels. Here, we report the development and implementation of a video-rate multiphoton microscope (VR-MPLSM) based on resonant galvanometer mirror scanning that is capable of recording at 30 frames per second and acquiring intravital multispectral images. We show that the design of the system can be readily implemented and is adaptable to various experimental models. As examples, we demonstrate the utility of the system to directly measure flow within tumors, capture metastatic cancer cells moving within the brain vasculature and cells in lymphatic vessels, and image acute responses to changes in a vascular network. VR-MPLSM thus has the potential to further advance intravital imaging and provide new insight into the biology of the tumor microenvironment. PMID:24353926

Multi-photon vertical cross-sectional imaging with a dynamically-balanced thin-film PZT z-axis microactuator.

PubMed

Choi, Jongsoo; Duan, Xiyu; Li, Haijun; Wang, Thomas D; Oldham, Kenn R

2017-10-01

Use of a thin-film piezoelectric microactuator for axial scanning during multi-photon vertical cross-sectional imaging is described. The actuator uses thin-film lead-zirconate-titanate (PZT) to generate upward displacement of a central mirror platform, micro-machined from a silicon-on-insulator (SOI) wafer to dimensions compatible with endoscopic imaging instruments. Device modeling in this paper focuses on existence of frequencies near device resonance producing vertical motion with minimal off-axis tilt even in the presence of multiple vibration modes and non-uniformity in fabrication outcomes. Operation near rear resonance permits large stroke lengths at low voltages relative to other vertical microactuators. Highly uniform vertical motion of the mirror platform is a key requirement for vertical cross-sectional imaging in the remote scan architecture being used for multi-photon instrument prototyping. The stage is installed in a benchtop testbed in combination with an electrostatic mirror that performs in-plane scanning. Vertical sectional images are acquired from 15 μm diameter beads and excised mouse colon tissue.

Resonantly enhanced method for generation of tunable, coherent vacuum ultraviolet radiation

DOEpatents

Glownia, James H.; Sander, Robert K.

1985-01-01

Carbon Monoxide vapor is used to generate coherent, tunable vacuum ultraviolet radiation by third-harmonic generation using a single tunable dye laser. The presence of a nearby electronic level resonantly enhances the nonlinear susceptibility of this molecule allowing efficient generation of the vuv light at modest pump laser intensities, thereby reducing the importance of a six-photon multiple-photon ionization process which is also resonantly enhanced by the same electronic level but to higher order. By choosing the pump radiation wavelength to be of shorter wavelength than individual vibronic levels used to extend tunability stepwise from 154.4 to 124.6 nm, and the intensity to be low enough, multiple-photon ionization can be eliminated. Excitation spectra of the third-harmonic emission output exhibit shifts to shorter wavelength and broadening with increasing CO pressure due to phase matching effects. Increasing the carbon monoxide pressure, therefore, allows the substantial filling in of gaps arising from the stepwise tuning thereby providing almost continuous tunability over the quoted range of wavelength emitted.

Resonantly enhanced method for generation of tunable, coherent vacuum-ultraviolet radiation

DOEpatents

Glownia, J.H.; Sander, R.K.

1982-06-29

Carbon Monoxide vapor is used to generate coherent, tunable vacuum ultraviolet radiation by third-harmonic generation using a single tunable dye laser. The presence of a nearby electronic level resonantly enhances the nonlinear susceptibility of this molecule allowing efficient generation of the vuv light at modest pump laser intensities, thereby reducing the importance of a six-photon multiple-photon ionization process which is also resonantly enhanced by the same electronic level but no higher order. By choosing the pump radiation wavelength to be of shorter wavelength than individual vibronic levels used to extend tunability stepwise from 154.4 to 124.6 nm, and the intensity to be low enough, multiple-photon ionization can be eliminated. Excitation spectra of the third-harmonic emission output exhibit shifts to shorter wavelength and broadening with increasing CO pressure due to phase matching effects. Increasing the carbon monoxide pressure, therefore, allows the substantial filling in of gaps arising from the stepwise tuning thereby providing almost continuous tunability over the quoted range of wavelength emitted.

Enhancing nonlinear energy deposition into transparent solids with an elliptically polarized and mid-IR heating laser pulse under two-color femtosecond impact

NASA Astrophysics Data System (ADS)

Potemkin, F. V.; Mareev, E. I.; Bezsudnova, Yu I.; Platonenko, V. T.; Bravy, B. G.; Gordienko, V. M.

2017-06-01

We report on an enhancement of deposited energy density of up to 10 kJ cm-3 inside transparent solids (fused silica and quartz) from using two-color µJ energy level tightly focused (NA  =  0.5) co-propagating linearly polarized seeding (visible, 0.62 µm) and elliptically polarized heating (near-IR, 1.24 µm) femtosecond laser pulses. The rise in temperature under constant volume causes pressure of up to 12 GPa. It has been shown experimentally and theoretically that the production of seeding electrons through multiphoton ionization by visible laser pulse paves the way for controllability of the energy deposition and laser-induced micromodification via carrier heating by delayed infrared laser pulses inside the material. The developed theoretical approach predicts that the deposited energy density will be enhanced by up to 14 kJ cm-3 when using longer (up to 5 µm) wavelengths for heating laser pulses inside transparent solids.

a Study of the Interaction of Atoms with Strong Laser Fields.

NASA Astrophysics Data System (ADS)

Edwards, Mark

1984-02-01

In this thesis three aspects of the interactions of atoms with high intensity laser fields were treated. All three were motivated by experiment. The first investigation was prompted by a recent experiment (Kruit et al. 1983) involving multiphoton ionization of Xe. In this experiment it was found that the photoelectron energy spectrum contained peaks which corresponded to the absorption of more than the minimum number of photons required to ionize the atom. The effective orders of nonlinearity, furthermore, showed a striking uniformity. These effects were investigated using a model approximation consisting of a single bound state and m continua. Simple analytic expressions were obtained for the quantities measured in the experiment and the limit m (--->) (INFIN) was obtained. The results showed good qualitative agreement with experiment. An experiment (Grove et al. 1977) designed to test a theoretical calculation of the dynamical Stark effect stimulated the second part of this thesis. When experimental conditions were varied slightly, strong field turn-on effects were observed in the resonance fluorescence spectrum from a two-level atom (TLA). This experimental result led to the present study of how an adiabatically and near-adiabatically changing field intensity affects the resonance fluorescence spectrum of a TLA. It was found that there is an asymmetry in the spectrum for off-resonance excitation produced because the field turn-on repopulates the dressed state that is depopulated by spontaneous emission. The experimental result was not explained by this result, however. The third part of this thesis was based on an experiment (Granneman and Van der Wiel 1976) which attempted to verify a perturbation calculation of the two-photon ionization cross section of Cs. A discrepancy of four orders of magnitude near a minimum in the cross section was found between theory and experiment. To explain this discrepancy it was suggested (Armstrong and Beers 1977) that the effective order of nonlinearity (k) for this process varied significantly around the minimum. The present study involves a perturbation calculation of k. It was found that k varies rapidly around the minimum, and that this variation should be experimentally observable for laser intensities of the order of tens of GW cm('-2).

Convoy electron emission from resonant coherently excited 390 MeV/u hydrogen-like Ar ions

NASA Astrophysics Data System (ADS)

Azuma, T.; Takabayashi, Y.; Ito, T.; Komaki, K.; Yamazaki, Y.; Takada, E.; Murakami, T.

2003-12-01

Energetic ions traveling through a single crystal are excited by an oscillating crystal field produced by a periodic arrangement of the atomic strings/planes, which is called Resonant Coherent Excitation (RCE). We have observed enhancement of convoy electron yields associated with RCE of 1s electron to the n=2 excited states of 390 MeV/u hydrogen-like Ar 17+ ions passing through a Si crystal in the (2 2¯ 0) planar channeling condition. Lost electrons from projectile ions due to ionization contribute to convoy electrons emitted in the forward direction with the same velocity as the projectile ions. With combination of a magnet and a thick Si solid-state detector, we measured the energy spectra of convoy electrons of about 200 keV emitted at 0°. The convoy electron yield as a function of the transition energy, i.e. the resonance profile, has a similar structure to the resonance profile observed through the ionized fraction of the emerging ions. It is explained by the fact that both enhancements are due to increase in the fraction of the excited states from which electrons are more easily ionized by target electron impact in the crystal than from the ground state.

Observation of ionization enhancement in two-color circularly polarized laser fields

NASA Astrophysics Data System (ADS)

Mancuso, Christopher A.; Dorney, Kevin M.; Hickstein, Daniel D.; Chaloupka, Jan L.; Tong, Xiao-Min; Ellis, Jennifer L.; Kapteyn, Henry C.; Murnane, Margaret M.

2017-08-01

When atoms are irradiated by two-color circularly polarized laser fields the resulting strong-field processes are dramatically different than when the same atoms are irradiated by a single-color ultrafast laser. For example, electrons can be driven in complex two-dimensional trajectories before rescattering or circularly polarized high harmonics can be generated, which was once thought impossible. Here, we show that two-color circularly polarized lasers also enable control over the ionization process itself and make a surprising finding: the ionization rate can be enhanced by up to 700 % simply by switching the relative helicity of the two-color circularly polarized laser field. This enhancement is experimentally observed in helium, argon, and krypton over a wide range of intensity ratios of the two-color field. We use a combination of advanced quantum and fully classical calculations to explain this ionization enhancement as resulting in part due to the increased density of excited states available for resonance-enhanced ionization in counter-rotating fields compared with co-rotating fields. In the future, this effect could be used to probe the excited state manifold of complex molecules.

Laser-Induced Ionization Efficiency Enhancement On A Filament For Thermal Ionization Mass Spectrometry

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

Siegfried, M.

2015-10-14

The evaluation of trace Uranium and Plutonium isotope ratios for nanogram to femtogram material quantities is a vital tool for nuclear counter-proliferation and safeguard activities. Thermal Ionization Mass Spectrometry (TIMS) is generally accepted as the state of the art technology for highly accurate and ultra-trace measurements of these actinide ratios. However, the very low TIMS ionization yield (typically less than 1%) leaves much room for improvement. Enhanced ionization of Nd and Sm from a TIMS filament was demonstrated using wavelength resonance with a nanosecond (pulse width) laser operating at 10 Hz when light was directed toward the filament.1 For thismore » study, femtosecond and picosecond laser capabilities were to be employed to study the dissociation and ionization mechanisms of actinides/lanthanides and measure the enhanced ionization of the metal of interest. Since the underlying chemistry of the actinide/lanthanide carbides produced and dissociated on a TIMS filament is not well understood, the experimental parameters affecting the photodissociation and photoionization with one and two laser beams were to be investigated.« less

Plasma effect on fast-electron-impact-ionization from 2p state of hydrogen-like ions

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

Qi, Y. Y.; Ning, L. N.; Wang, J. G.

2013-12-15

Plasma effects on the high-energy electron-impact ionization process from 2p orbital of Hydrogen-like ions embedded in weakly coupled plasmas are investigated in the first Born approximation. The plasma screening of the Coulomb interaction between charged particles is represented by the Debye Hückel model. The screening of Coulomb interactions decreases the ionization energies and varies the wave functions for not only the bound orbital but also the continuum; the number of the summation for the angular-momentum states in the generalized oscillator strength densities is reduced with the plasma screening stronger when the ratio of ε/I{sub 2p} (I{sub 2p} is the ionizationmore » energy of 2p state and ε is the energy of the continuum electron) is kept, and then the contribution from the lower-angular-momentum states dominates the generalized oscillator strength densities, so the threshold phenomenon in the generalized oscillator strength densities and the double differential cross sections are remarkable: The accessional minima, the outstanding enhancement, and the resonance peaks emerge a certain energy region, whose energy position and width are related to the vicinity between δ and the critical value δ{sub nl}{sup c}, corresponding to the special plasma condition when the bound state |nl just enters the continuum; the multiple virtual-state enhancement and the multiple shape resonances in a certain energy domain also appear in the single differential cross section whenever the plasma screening parameter passes through a critical value δ{sub nl}{sup c}, which is similar to the photo-ionization process but different from it, where the dipole transition only happens, but multi-pole transition will occur in the electron-impact ionization process, so its multiple virtual-state enhancements and the multiple shape resonances appear more frequently than the photo-ionization process.« less

ARTICLES: Variation of the absorption cross section of high-power infrared laser radiation in homologous series of CnH2n+1OH molecules

NASA Astrophysics Data System (ADS)

Bagratashvili, Viktor N.; Brodskaya, E. A.; Vereshchagina, Lyudmila N.; Kuz'min, M. V.; Osmanov, R. R.; Putilin, F. N.; Stuchebryukhov, A. A.

1984-11-01

An experimental investigation was made of variation of the characteristics of infrared multiphoton absorption in a homologous series of CnH2n+1OH alcohols (n = 1-5) excited with CO2 laser pulses. The dependences of the energy absorbed by the molecules on the frequency and energy density of laser radiation were determined by the optoacoustic method. It was found that the multiphoton absorption cross section decreases on increase in the radiation energy density at a rate which becomes slower on increase in the molecular size. A model is proposed for multiphoton excitation of molecules in a homologous series. This model is based on an analysis of a resonant mode interacting with the infrared radiation field and coupled to a reservoir of modes that do not interact with the field. The model predicts correctly the change in the multiphoton absorption cross section on increase in the number of the degrees of freedom of a molecule.

Organic chemical analysis on a microscopic scale using two-step laser desorption/laser ionization mass spectrometry

NASA Technical Reports Server (NTRS)

Kovalenko, L. J.; Philippoz, J.-M.; Bucenell, J. R.; Zenobi, R.; Zare, R. N.

1991-01-01

The distribution of PAHs in the Allende meteorite has been measured using two-step laser desorption and laser multiphoton-ionization mass spectrometry. This method enables in situ analysis (with a spatial resolution of 1 mm or better) of selected organic molecules. Results show that PAH concentrations are locally high compared to the average concentration found by analysis of pulverized samples, and are found primarily in the fine-grained matrix; no PAHs were detected in the interiors of individual chondrules at the detection limit (about 0.05 ppm).

Experimental investigation of strong-field-ionization theories for laser fields from visible to midinfrared frequencies

NASA Astrophysics Data System (ADS)

Lai, Yu Hang; Xu, Junliang; Szafruga, Urszula B.; Talbert, Bradford K.; Gong, Xiaowei; Zhang, Kaikai; Fuest, Harald; Kling, Matthias F.; Blaga, Cosmin I.; Agostini, Pierre; DiMauro, Louis F.

2017-12-01

Strong-field-ionization yield versus intensity is investigated for various atomic targets (Ne, Ar, Kr, Xe, Na, K, Zn, and Mg) and light polarization from visible to mid-infrared (0.4-4 μ m ), from multiphoton to tunneling regimes. The experimental findings (normalized yield vs intensity, ratio of circular to linear polarization and saturation intensities) are compared to the theoretical models of Perelomov-Popov-Terent'ev (PPT) and Ammosov-Delone-Krainov (ADK). While PPT is generally satisfactory, ADK validity is found, as expected, to be much more limited.

Searching for Axionlike Particles with Ultraperipheral Heavy-Ion Collisions.

PubMed

Knapen, Simon; Lin, Tongyan; Lou, Hou Keong; Melia, Tom

2017-04-28

We show that ultraperipheral heavy-ion collisions at the Large Hadron Collider (LHC) can be used to search for axionlike particles with mass below 100 GeV. The Z^{4} enhanced photon-photon luminosity from the ions provides a large exclusive production rate, with a signature of a resonant pair of back-to-back photons and no other activity in the detector. In addition, we present both new and updated limits from recasting multiphoton searches at LEP II and the LHC, which are more stringent than those currently in the literature for the mass range 100 MeV to 100 GeV.

Below-threshold harmonic generation from strong non-uniform fields

NASA Astrophysics Data System (ADS)

Yavuz, I.

2017-10-01

Strong-field photoemission below the ionization threshold is a rich/complex region where atomic emission and harmonic generation may coexist. We studied the mechanism of below-threshold harmonics (BTH) from spatially non-uniform local fields near the metallic nanostructures. Discrete harmonics are generated due to the broken inversion symmetry, suggesting enriched coherent emission in the vuv frequency range. Through the numerical solution of the time-dependent Schrödinger equation, we investigate wavelength and intensity dependence of BTH. Wavelength dependence identifies counter-regular resonances; individual contributions from the multi-photon emission and channel-closing effects due to quantum path interferences. In order to understand the underlying mechanism of BTH, we devised a generalized semi-classical model, including the influence of Coulomb and non-uniform field interactions. As in uniform fields, Coulomb potential in non-uniform fields is the determinant of BTH; we observed that the generation of BTH are due to returning trajectories with negative energies. Due to large distance effectiveness of the non-uniformity, only long trajectories are noticeably affected.

The laser lightning rod system: thunderstorm domestication.

PubMed

Ball, L M

1974-10-01

An unusual application of the laser, namely protection of life and property from lightning, is described. The device relies on multiphoton ionization in mode-locked beams, rather than on collisional (avalanche) electron production. Feasibility is demonstrated numerically, and relevant principles explained. A method of mobile deployment is mentioned, by which economic (as opposed to scientific) feasibility might be achieved.

Ultraviolet photodissociation dynamics of the benzyl radical.

PubMed

Song, Yu; Zheng, Xianfeng; Lucas, Michael; Zhang, Jingsong

2011-05-14

Ultraviolet (UV) photodissociation dynamics of jet-cooled benzyl radical via the 4(2)B(2) electronically excited state is studied in the photolysis wavelength region of 228 to 270 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance enhanced multiphoton ionization (REMPI) techniques. In this wavelength region, H-atom photofragment yield (PFY) spectra are obtained using ethylbenzene and benzyl chloride as the precursors of benzyl radical, and they have a broad peak centered around 254 nm and are in a good agreement with the previous UV absorption spectra of benzyl. The H + C(7)H(6) product translational energy distributions, P(E(T))s, are derived from the H-atom TOF spectra. The P(E(T)) distributions peak near 5.5 kcal mol(-1), and the fraction of average translational energy in the total excess energy, , is ∼0.3. The P(E(T))s indicate the production of fulvenallene + H, which was suggested by recent theoretical studies. The H-atom product angular distribution is isotropic, with the anisotropy parameter β ≈ 0. The H/D product ratios from isotope labeling studies using C(6)H(5)CD(2) and C(6)D(5)CH(2) are reasonably close to the statistical H/D ratios, suggesting that the H/D atoms are scrambled in the photodissociation of benzyl. The dissociation mechanism is consistent with internal conversion of the electronically excited benzyl followed by unimolecular decomposition of the hot benzyl radical on the ground state.

Use of REMPI-TOFMS for real-time measurement of trace aromatics during operation of aircraft ground equipment

NASA Astrophysics Data System (ADS)

Gullett, Brian; Touati, Abderrahmane; Oudejans, Lukas

Emissions of aromatic air toxics from aircraft ground equipment (AGE) were measured with a resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) system consisting of a pulsed solid state laser for photoionization and a TOFMS for mass discrimination. This instrument was capable of characterizing turbine emissions and the effect of varying load operations on pollutant production. REMPI-TOFMS is capable of high selectivity and low detection limits (part per trillion to part per billion) in real time (1 s resolution). Hazardous air pollutants and criteria pollutants were measured during startups and idle and full load operations. Measurements of compounds such as benzene, toluene, ethylbenzene, xylenes, styrene, and polycyclic aromatic hydrocarbons compared well with standard methods. Startup emissions from the AGE data showed persistent concentrations of pollutants, unlike those from a diesel generator, where a sharp spike in emissions rapidly declined to steady state levels. The time-resolved responses of air toxics concentrations varied significantly by source, complicating efforts to minimize these emissions with common operating prescriptions. The time-resolved measurements showed that pollutant concentrations decline (up to 5×) in a species-specific manner over the course of multiple hours of operation, complicating determination of accurate and precise emission factors via standard extractive sampling. Correlations of air toxic concentrations with more commonly measured pollutants such as CO or PM were poor due to the relatively greater changes in the measured toxics' concentrations.

Photodissociation dynamics of bromoiodomethane from the first and second absorption bands. A combined velocity map and slice imaging study.

PubMed

Marggi Poullain, Sonia; Chicharro, David V; Navarro, Eduardo; Rubio-Lago, Luis; González-Vázquez, Jesús; Bañares, Luis

2018-01-31

The photodissociation dynamics of bromoiodomethane (CH 2 BrI) have been investigated at the maximum of the first A and second A' absorption bands, at 266 and 210 nm excitation wavelengths, respectively, using velocity map and slice imaging techniques in combination with a probe detection of both iodine and bromine fragments, I( 2 P 3/2 ), I*( 2 P 1/2 ), Br( 2 P 3/2 ) and Br*( 2 P 1/2 ) via (2 + 1) resonance enhanced multiphoton ionization. Experimental results, i.e. translational energy and angular distributions, are reported and discussed in conjunction with high level ab initio calculations of potential energy curves and absorption spectra. The results indicate that in the A-band, direct dissociation through the 5A' excited state leads to the I( 2 P 3/2 ) channel while I*( 2 P 1/2 ) atoms are produced via the 5A' → 4A'/4A'' nonadiabatic crossing. The presence of Br and Br* fragments upon excitation to the A-band is attributed to indirect dissociation via a curve crossing between the 5A' with upper excited states such as the 9A'. The A'-band is characterized by a strong photoselectivity leading exclusively to the Br( 2 P 3/2 ) and Br*( 2 P 1/2 ) channels, which are likely produced by dissociation through the 9A' excited state. Avoided crossings between several excited states from both the A and A' bands entangle however the possible reaction pathways.

The visible spectrum of zirconium dioxide, ZrO2

NASA Astrophysics Data System (ADS)

Le, Anh; Steimle, Timothy C.; Gupta, Varun; Rice, Corey A.; Maier, John P.; Lin, Sheng H.; Lin, Chih-Kai

2011-09-01

The electronic spectrum of a cold molecular beam of zirconium dioxide, ZrO2, has been investigated using laser induced fluorescence (LIF) in the region from 17 000 cm-1 to 18 800 cm-1 and by mass-resolved resonance enhanced multi-photon ionization (REMPI) spectroscopy from 17 000 cm-1-21 000 cm-1. The LIF and REMPI spectra are assigned to progressions in the tilde A{^1}B_2(ν1, ν2, ν3) ← tilde X{^1}A_1(0, 0, 0) transitions. Dispersed fluorescence from 13 bands was recorded and analyzed to produce harmonic vibrational parameters for the tilde X{^1}A_1 state of ω1 = 898(1) cm-1, ω2 = 287(2) cm-1, and ω3 = 808(3) cm-1. The observed transition frequencies of 45 bands in the LIF and REMPI spectra produce origin and harmonic vibrational parameters for the tilde A{^1}B_2 state of Te = 16 307(8) cm-1, ω1 = 819(3) cm-1, ω2 = 149(3) cm-1, and ω3 = 518(4) cm-1. The spectra were modeled using a normal coordinate analysis and Franck-Condon factor predictions. The structures, harmonic vibrational frequencies, and the potential energies as a function of bending angle for the tilde A{^1}B_2 and tilde X{^1}A_1 states are predicted using time-dependent density functional theory, complete active space self-consistent field, and related first-principle calculations. A comparison with isovalent TiO2 is made.

Ultralow-threshold multiphoton-pumped lasing from colloidal nanoplatelets in solution

PubMed Central

Li, Mingjie; Zhi, Min; Zhu, Hai; Wu, Wen-Ya; Xu, Qing-Hua; Jhon, Mark Hyunpong; Chan, Yinthai

2015-01-01

Although multiphoton-pumped lasing from a solution of chromophores is important in the emerging fields of nonlinear optofluidics and bio-photonics, conventionally used organic dyes are often rendered unsuitable because of relatively small multiphoton absorption cross-sections and low photostability. Here, we demonstrate highly photostable, ultralow-threshold multiphoton-pumped biexcitonic lasing from a solution of colloidal CdSe/CdS nanoplatelets within a cuvette-based Fabry–Pérot optical resonator. We find that colloidal nanoplatelets surprisingly exhibit an optimal lateral size that minimizes lasing threshold. These nanoplatelets possess very large gain cross-sections of 7.3 × 10−14 cm2 and ultralow lasing thresholds of 1.2 and 4.3 mJ cm−2 under two-photon (λexc=800 nm) and three-photon (λexc=1.3 μm) excitation, respectively. The highly polarized emission from the nanoplatelet laser shows no significant photodegradation over 107 laser shots. These findings constitute a more comprehensive understanding of the utility of colloidal semiconductor nanoparticles as the gain medium in high-performance frequency-upconversion liquid lasers. PMID:26419950

High-Energy Laser Interaction with Gases, Droplets, and Bulk Liquids.

NASA Astrophysics Data System (ADS)

Jarzembski, Maurice Anthony

Breakdown threshold intensities (I_ {rm TH}) were measured as functions of wavelengths and pressure for air, He, Ar, and Xe using a Nd:YAG pulsed laser. Multiphoton absorption dominates in the UV and cascade collision ionization dominates in the IR; however, both can be affected by other electron gain and loss processes. Presence of droplets lowers breakdown of gases due to field enhancements. Breakdown is initiated either in the droplet material or in the gas. At lambda = 0.532mum for a 50 μm dia. water droplet in He, Ar, and air for p < 800 Torr, breakdown occurs inside the droplet and is independent of gas pressure. For droplet -in-Xe, at p < 140 Torr breakdown occurs inside the droplet and is independent of gas pressure. For droplet-in-Xe, at p < 140 Torr breakdown occurs inside the droplet but at p > 140 Torr, breakdown occurs outside the droplet and is dependent on gas pressure. Pressure dependence of breakdown was observed for 120mum dia. water droplets in Ar at p > 400 Torr. The required intensity for breakdown of droplet depends on I_{ rm TH} of bulk liquid and the effective field enhancement created by the droplet. The I _{rm TH} of droplet-in-air provides an upper limit to the propagation of a high energy laser beam in the atmosphere containing particles. By geometrical optics approach, a significant field enhancement located at the critical ring region, encircling the axis of the sphere in the forward direction at angle theta_{c}, was discovered where nonlinear processes can occur. This was confirmed experimentally and by Mie theory. Field enhancements calculated at the critical ring for water droplets of different sizes agree well with measurements. For a droplet of given size and real refractive index, the effective field enhancement and the volume over which it occurs are two important factors governing the occurrence of breakdown in droplets for both off resonance and on resonance conditions. Measurements of wavelength dependence of breakdown showed that in the UV, I_{rm TH} for droplets and bulk liquids were comparable and lower by few orders of magnitude from that of air. Transmittance and reflectance of bulk liquids in the UV change with intensity implying absorption due to nonlinear processes and consequent increase in the imaginary part of the refractive index of the liquids. In the IR, I_{rm TH} of air and bulk liquids are comparable but for droplets are considerably lower due to field enhancement.

A new high intensity and short-pulse molecular beam valve

NASA Astrophysics Data System (ADS)

Yan, B.; Claus, P. F. H.; van Oorschot, B. G. M.; Gerritsen, L.; Eppink, A. T. J. B.; van de Meerakker, S. Y. T.; Parker, D. H.

2013-02-01

In this paper, we report on the design and performance of a new home-built pulsed gas valve, which we refer to as the Nijmegen Pulsed Valve (NPV). The main output characteristics include a short pulse width (as short as 20 μs) combined with operating rates up to 30 Hz. The operation principle of the NPV is based on the Lorentz force created by a pulsed current passing through an aluminum strip located within a magnetic field, which opens the nozzle periodically. The amplitude of displacement of the opening mechanism is sufficient to allow the use of nozzles with up to 1.0 mm diameter. To investigate the performance of the valve, several characterizations were performed with different experimental methods. First, a fast ionization gauge was used to measure the beam intensity of the free jet emanating from the NPV. We compare free jets from the NPV with those from several other pulsed valves in current use in our laboratory. Results showed that a high intensity and short pulse-length beam could be generated by the new valve. Second, the NPV was tested in combination with a skimmer, where resonance enhanced multiphoton ionization combined with velocity map imaging was used to show that the NPV was able to produce a pulsed molecular beam with short pulse duration (˜20 μs using 0.1% NO/He at 6 bars) and low rotational temperature (˜1 K using 0.5% NO/Ar at 6 bars). Third, a novel two-point pump-probe method was employed which we label double delay scan. This method allows a full kinematic characterization of the molecular beam, including accurate speed ratios at different temporal positions. It was found that the speed ratio was maximum (S = 50 using 0.1% NO/He at 3 bars) at the peak position of the molecular beam and decreased when it was on the leading or falling edge.

Simulation of deleterious processes in a static-cell diode pumped alkali laser

NASA Astrophysics Data System (ADS)

Oliker, Benjamin Q.; Haiducek, John D.; Hostutler, David A.; Pitz, Greg A.; Rudolph, Wolfgang; Madden, Timothy J.

2014-02-01

The complex interactions in a diode pumped alkali laser (DPAL) gain cell provide opportunities for multiple deleterious processes to occur. Effects that may be attributable to deleterious processes have been observed experimentally in a cesium static-cell DPAL at the United States Air Force Academy [B.V. Zhdanov, J. Sell, R.J. Knize, "Multiple laser diode array pumped Cs laser with 48 W output power," Electronics Letters, 44, 9 (2008)]. The power output in the experiment was seen to go through a "roll-over"; the maximum power output was obtained with about 70 W of pump power, then power output decreased as the pump power was increased beyond this point. Research to determine the deleterious processes that caused this result has been done at the Air Force Research Laboratory utilizing physically detailed simulation. The simulations utilized coupled computational fluid dynamics (CFD) and optics solvers, which were three-dimensional and time-dependent. The CFD code used a cell-centered, conservative, finite-volume discretization of the integral form of the Navier-Stokes equations. It included thermal energy transport and mass conservation, which accounted for chemical reactions and state kinetics. Optical models included pumping, lasing, and fluorescence. The deleterious effects investigated were: alkali number density decrease in high temperature regions, convective flow, pressure broadening and shifting of the absorption lineshape including hyperfine structure, radiative decay, quenching, energy pooling, off-resonant absorption, Penning ionization, photoionization, radiative recombination, three-body recombination due to free electron and buffer gas collisions, ambipolar diffusion, thermal aberration, dissociative recombination, multi-photon ionization, alkali-hydrocarbon reactions, and electron impact ionization.

Level crossings in the ionization of H(2) Rydberg molecules at a metal surface.

PubMed

McCormack, E A; Ford, M S; Softley, T P

2010-10-28

The ionization of H(2) Rydberg states at a metal surface is investigated using a molecular beam incident at grazing incidence on a gold surface. The H(2) molecules, excited by stepwise two-color laser excitation, are selected in each of the accessible Stark eigenstates of the N(+) = 2, n = 17 Rydberg manifold in turn and the ionization at the surface is characterized by applying a field to extract the ions formed. Profiles of extracted ion signal versus applied field show resonances that can be simulated by assuming an enhancement of surface ionization at fields corresponding to energy-level crossings between the populated N(+) = 2 manifold and the near-degenerate N(+) = 0 Stark manifolds. It is concluded that the slow (microsecond time scale) rotation-electronic energy transfer to N(+) = 0 states occurring at these crossings takes place in the time interval following application of the field ramp when the molecule is still distant from, and unperturbed by, the surface. However, the energy levels are strongly perturbed by image-dipole interactions as the molecule approaches close to the surface, leading to additional energy-level crossings. Adiabatic behavior at such crossings affects the intensity of the observed resonances in the surface ionization signal but not their field positions. Resonances are also observed in the surface ionization profiles at fields above the field-ionization threshold; some of these show asymmetric "Fano-type" line shapes due to quantum interference in the nonradiative coupling to degenerate bound and continuum states.

Nonlinear optical effects in semi-polar GaN micro-cavity emitter

NASA Astrophysics Data System (ADS)

Butler, Sween; Jiang, Hongxing; Lin, Jingyu; Neogi, Arup

Nonlinear optical (NLO) response of low dimensional emitters is of current interest because of the need for active elements in photonic applications. NLO effects in a selectively grown array of semi-polar GaN microcavity structures offer a promising route toward devices for integrated optical circuitry in optoelectronics and photonics field. Localized spatial excitation of a single hexagonal GaN microcavity with semipolar facets formed by selective area growth was optimized for nonlinear optical light generation due to second harmonic generation (SHG) and multi-photon luminescence(MPL). Multi-photon transition induced by tightly focused femtosecond NIR incident field results in ultra-violet and yellow luminescence for excitations above and below half bandgap energy, whereas SHG was observed for below half bandgap energy. We show that color and coherence of the light generation from the emitter can be controlled by selective onset of the nonlinear process which depends not only on the incident laser energy and intensity but also on the geometry of the microcavity. Quasi-WGM like modes were observed for off-resonant excitations from the GaN microcavity resulting in enhanced SHG. The directionality of MPL and SHG will be presented as a function of the pump polarization.

Insights on proximity effect and multiphoton induced luminescence from gold nanospheres in far field optical microscopy

NASA Astrophysics Data System (ADS)

Borglin, Johan; Guldbrand, Stina; Evenbratt, Hanne; Kirejev, Vladimir; Grönbeck, Henrik; Ericson, Marica B.

2015-12-01

Gold nanoparticles can be visualized in far-field multiphoton laser-scanning microscopy (MPM) based on the phenomena of multiphoton induced luminescence (MIL). This is of interest for biomedical applications, e.g., for cancer diagnostics, as MPM allows for working in the near-infrared (NIR) optical window of tissue. It is well known that the aggregation of particles causes a redshift of the plasmon resonance, but its implications for MIL applying far-field MPM should be further exploited. Here, we explore MIL from 10 nm gold nanospheres that are chemically deposited on glass substrates in controlled coverage gradients using MPM operating in NIR range. The substrates enable studies of MIL as a function of inter-particle distance and clustering. It was shown that MIL was only detected from areas on the substrates where the particle spacing was less than one particle diameter, or where the particles have aggregated. The results are interpreted in the context that the underlying physical phenomenon of MIL is a sequential two-photon absorption process, where the first event is driven by the plasmon resonance. It is evident that gold nanospheres in this size range have to be closely spaced or clustered to exhibit detectable MIL using far-field MPM operating in the NIR region.

Insights on proximity effect and multiphoton induced luminescence from gold nanospheres in far field optical microscopy

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

Borglin, Johan; Department of Physics, University of Gothenburg, Kemivägen 10, 412 96 Gothenburg; Guldbrand, Stina

Gold nanoparticles can be visualized in far-field multiphoton laser-scanning microscopy (MPM) based on the phenomena of multiphoton induced luminescence (MIL). This is of interest for biomedical applications, e.g., for cancer diagnostics, as MPM allows for working in the near-infrared (NIR) optical window of tissue. It is well known that the aggregation of particles causes a redshift of the plasmon resonance, but its implications for MIL applying far-field MPM should be further exploited. Here, we explore MIL from 10 nm gold nanospheres that are chemically deposited on glass substrates in controlled coverage gradients using MPM operating in NIR range. The substrates enablemore » studies of MIL as a function of inter-particle distance and clustering. It was shown that MIL was only detected from areas on the substrates where the particle spacing was less than one particle diameter, or where the particles have aggregated. The results are interpreted in the context that the underlying physical phenomenon of MIL is a sequential two-photon absorption process, where the first event is driven by the plasmon resonance. It is evident that gold nanospheres in this size range have to be closely spaced or clustered to exhibit detectable MIL using far-field MPM operating in the NIR region.« less

Dynamics of focused femtosecond laser pulse during photodisruption of crystalline lens

NASA Astrophysics Data System (ADS)

Gupta, Pradeep Kumar; Singh, Ram Kishor; Sharma, R. P.

2018-04-01

Propagation of laser pulses of femtosecond time duration (focused through a focusing lens inside the crystalline lens) has been investigated in this paper. Transverse beam diffraction, group velocity dispersion, graded refractive index structure of the crystalline lens, self-focusing, and photodisruption in which plasma is formed due to the high intensity of laser pulses through multiphoton ionization have been taken into account. The model equations are the modified nonlinear Schrödinger equation along with a rate equation that takes care of plasma generation. A close analysis of model equations suggests that the femtosecond laser pulse duration is critical to the breakdown in the lens. Our numerical simulations reveal that the combined effect of self-focusing and multiphoton ionization provides the breakdown threshold. During the focusing of femtosecond laser pulses, additional spatial pulse splitting arises along with temporal splitting. This splitting of laser pulses arises on account of self-focusing, laser induced breakdown, and group velocity distribution, which modifies the shape of laser pulses. The importance of the present study in cavitation bubble generation to improve the elasticity of the eye lens has also been discussed in this paper.

Robust Distant Entanglement Generation Using Coherent Multiphoton Scattering

NASA Astrophysics Data System (ADS)

Chan, Ching-Kit; Sham, L. J.

2013-02-01

We describe a protocol to entangle two qubits at a distance by using resonance fluorescence. The scheme makes use of the postselection of large and distinguishable fluorescence signals corresponding to entangled and unentangled qubit states and has the merits of both high success probability and high entanglement fidelity owing to the multiphoton nature. Our result shows that the entanglement generation is robust against photon fluctuations in the fluorescence signals for a wide range of driving fields. We also demonstrate that this new protocol has an average entanglement duration within the decoherence time of corresponding qubit systems, based on current experimental photon efficiency.

Robust distant entanglement generation using coherent multiphoton scattering.

PubMed

Chan, Ching-Kit; Sham, L J

2013-02-15

We describe a protocol to entangle two qubits at a distance by using resonance fluorescence. The scheme makes use of the postselection of large and distinguishable fluorescence signals corresponding to entangled and unentangled qubit states and has the merits of both high success probability and high entanglement fidelity owing to the multiphoton nature. Our result shows that the entanglement generation is robust against photon fluctuations in the fluorescence signals for a wide range of driving fields. We also demonstrate that this new protocol has an average entanglement duration within the decoherence time of corresponding qubit systems, based on current experimental photon efficiency.

Quasi-lattices of qubits for generating inequivalent multipartite entanglements

NASA Astrophysics Data System (ADS)

Ian, Hou

2016-06-01

The mesoscopic scale of superconducting qubits makes their inter-spacings comparable to the scale of wavelength of a circuit cavity field to which they commonly couple. This comparability results in inhomogeneous coupling strengths for each qubit and hence asynchronous Rabi excitation cycles among the qubits that form a quasi-lattice. We find that such inhomogeneous coupling benefits the formation of multi-photon resonances between the single-mode cavity field and the quasi-lattice. The multi-photon resonances lead, in turn, to the simultaneous generation of inequivalent |\\text{GHZ}> and |W> types of multipartite entanglement states, which are not transformable to each other through local operations with classical communications. Applying the model on the 3-qubit quasi-lattice and using the entanglement measures of both concurrence and 3-tangle, we verify that the inhomogeneous coupling specifically promotes the generation of the totally inseparable |\\text{GHZ}> state.

Oleic acid-enhanced transdermal delivery pathways of fluorescent nanoparticles

NASA Astrophysics Data System (ADS)

Lo, Wen; Ghazaryan, Ara; Tso, Chien-Hsin; Hu, Po-Sheng; Chen, Wei-Liang; Kuo, Tsung-Rong; Lin, Sung-Jan; Chen, Shean-Jen; Chen, Chia-Chun; Dong, Chen-Yuan

2012-05-01

Transdermal delivery of nanocarriers provides an alternative pathway to transport therapeutic agents, alleviating pain, improving compliance of patients, and increasing overall effectiveness of delivery. In this work, enhancement of transdermal delivery of fluorescent nanoparticles and sulforhodamine B with assistance of oleic acid was visualized utilizing multiphoton microscopy (MPM) and analyzed quantitatively using multi-photon excitation-induced fluorescent signals. Results of MPM imaging and MPM intensity-based spatial depth-dependent analysis showed that oleic acid is effective in facilitating transdermal delivery of nanoparticles.

Investigation of ionized metal flux in enhanced high power impulse magnetron sputtering discharges

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

Stranak, Vitezslav, E-mail: stranak@prf.jcu.cz; Hubicka, Zdenek; Cada, Martin

2014-04-21

The metal ionized flux fraction and production of double charged metal ions Me{sup 2+} of different materials (Al, Cu, Fe, Ti) by High Power Impulse Magnetron Sputtering (HiPIMS) operated with and without a pre-ionization assistance is compared in the paper. The Electron Cyclotron Wave Resonance (ECWR) discharge was employed as the pre-ionization agent providing a seed of charge in the idle time of HiPIMS pulses. A modified grid-free biased quartz crystal microbalance was used to estimate the metal ionized flux fraction ξ. The energy-resolved mass spectrometry served as a complementary method to distinguish particular ion contributions to the total ionizedmore » flux onto the substrate. The ratio between densities of doubly Me{sup 2+} and singly Me{sup +} charged metal ions was determined. It is shown that ECWR assistance enhances Me{sup 2+} production with respect of absorbed rf-power. The ECWR discharge also increases the metal ionized flux fraction of about 30% especially in the region of lower pressures. Further, the suppression of the gas rarefaction effect due to enhanced secondary electron emission of Me{sup 2+} was observed.« less

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

Barc, B.; Ryszka, M.; Spurrell, J.

Multi-photon ionization (MPI) of the RNA base uracil has been studied in the wavelength range 220–270 nm, coinciding with excitation to the S{sub 2}(ππ*) state. A fragment ion at m/z = 84 was produced by 2-photon absorption at wavelengths ≤232 nm and assigned to C{sub 3}H{sub 4}N{sub 2}O{sup +} following CO abstraction. This ion has not been observed in alternative dissociative ionization processes (notably electron impact) and its threshold is close to recent calculations of the minimum activation energy for a ring opening conical intersection to a σ(n-π)π* closed shell state. Moreover, the predicted ring opening transition leaves a COmore » group at one end of the isomer, apparently vulnerable to abstraction. An MPI mass spectrum of uracil-water clusters is presented for the first time and compared with an equivalent dry measurement. Hydration enhances certain fragment ion pathways (particularly C{sub 3}H{sub 3}NO{sup +}) but represses C{sub 3}H{sub 4}N{sub 2}O{sup +} production. This indicates that hydrogen bonding to water stabilizes uracil with respect to neutral excited-state ring opening.« less

Wavelength Dependence of Nanosecond IR Laser-Induced Breakdown in Water: Evidence for Multiphoton Initiation via an Intermediate State

DTIC Science & Technology

2015-04-29

bubble generation and shock wave emission in water for femtosecond to nanosecond laser pulses . ...breakdown threshold in water for nanosecond (ns) IR laser pulses . Avalanche ionization (AI) is the most powerful mechanism driving IR ns laser-induced...acknowledged that femtosecond (fs) and picosecond (ps) IR breakdown is initiated by photoionization because ultrashort pulses are sufficiently

Analysis of Parent/Nitrated Polycyclic Aromatic Hydrocarbons in Particulate Matter 2.5 Based on Femtosecond Ionization Mass Spectrometry.

PubMed

Itouyama, Noboru; Matsui, Taiki; Yamamoto, Shigekazu; Imasaka, Tomoko; Imasaka, Totaro

2016-02-01

Particulate matter 2.5 (PM2.5), collected from ambient air in Fukuoka City, was analyzed by gas chromatography combined with multiphoton ionization mass spectrometry using an ultraviolet femtosecond laser (267 nm) as the ionization source. Numerous parent polycyclic aromatic hydrocarbons (PPAHs) were observed in a sample extracted from PM2.5, and their concentrations were determined to be in the range from 30 to 190 pg/m(3) for heavy PPAHs. Standard samples of nitrated polycyclic aromatic hydrocarbons (NPAHs) were examined, and the limits of detection were determined to be in the picogram range. The concentration of NPAH adsorbed on PM2.5 in the air was less than 900-1300 pg/m(3). Graphical Abstract ᅟ.

Impact of Coulomb potential on peak structures arising in momentum and low-energy photoelectron spectra produced in strong-field ionization of laser-irradiated atoms

NASA Astrophysics Data System (ADS)

Pyak, P. E.; Usachenko, V. I.

2018-03-01

The phenomenon of pronounced peak structure(s) of longitudinal momentum distributions as well as a spike-like structure of low-energy spectra of photoelectrons emitted from laser-irradiated Ar and Ne atoms in a single ionization process is theoretically studied in the tunneling and multiphoton regimes of ionization. The problem is addressed assuming only the direct above-threshold ionization (ATI) as a physical mechanism underlying the phenomenon under consideration (viz. solely contributing to observed photoelectron momentum distributions (PMD)) and using the Coulomb-Volkov (CV) ansatz within the frame of conventional strong-field approximation (SFA) applied in the length-gauge formulation. The developed CV-SFA approach also incorporates the density functional theory essentially exploited for numerical composition of initial (laser-free) atomic state(s) constructed from atomic orbitals of Gaussian type. Our presented CV-SFA based (and laser focal-volume averaged) calculation results proved to be well reproducing both the pronounced double-peak and/or ATI-like multi-peak structure(s) experimentally observed in longitudinal PMD under conditions of tunneling and/or multiphoton regime, respectively. In addition, our CV-SFA results presented for tunneling regime also suggest and remarkably reproduce a pronounced structure observed in relevant experiments as a ‘spike-like’ enhanced maximum arising in low-energy region (around the value of about 1 eV) of photoelectron spectra. The latter consistency allows to identify and interpret these results as the so-called low-energy structure (LES) since the phenomenon proved to appear as the most prominent if the influence of Coulomb potential on photoelectron continuum states is maximally taken into account under calculations (viz. if the parameter Z in CV’s functions is put equal to 1). Moreover, the calculated LES proved to correspond (viz., established as closely related) to the mentioned double-peak structure arising in the low-momentum region ({p}| | ≤slant | 0.2| a.u.) of longitudinal PMDs calculated under condition of the tunneling regime. Thus, the phenomena under consideration can be well understood and adequately interpreted beyond the terms and/or concepts of various different alternative strong-field approaches and models (such as e.g., extensively invoked and exploited nowadays though, more sophisticated SFA-based ‘rescattering’ mechanism) compared to which, the currently applied CV-SFA model (through the same underlying physical mechanism of solely direct ATI suggested) is additionally able to provide and reveal an intimate and transparent interrelation between the phenomena of LES and double-peak structure arising in PMDs observed in the tunneling regime.

A multiphoton objective design with incorporated beam splitter for enhanced fluorescence collection

PubMed Central

McMullen, Jesse D.; Zipfel, Warren R.

2010-01-01

We present a de novo design of an objective for use in multi-photon (MPM) and second harmonic generation (SHG) microscopy. This objective was designed to have a large field of view (FOV), while maintaining a moderate numerical aperture (NA) and relative straight forward construction. A dichroic beam splitter was incorporated within the objective itself allowing for an increase in the front aperture of the objective and corresponding enhancement of the solid angle of collected emission by an order of magnitude over existing designs. PMID:20389554

A multiphoton objective design with incorporated beam splitter for enhanced fluorescence collection.

PubMed

McMullen, Jesse D; Zipfel, Warren R

2010-03-15

We present a de novo design of an objective for use in multi-photon (MPM) and second harmonic generation (SHG) microscopy. This objective was designed to have a large field of view (FOV), while maintaining a moderate numerical aperture (NA) and relative straight forward construction. A dichroic beam splitter was incorporated within the objective itself allowing for an increase in the front aperture of the objective and corresponding enhancement of the solid angle of collected emission by an order of magnitude over existing designs.

Multiple-photon excitation of nitrogen vacancy centers in diamond

NASA Astrophysics Data System (ADS)

Ji, Peng; Balili, R.; Beaumariage, J.; Mukherjee, S.; Snoke, D.; Dutt, M. V. Gurudev

2018-04-01

We report the observation of multiphoton photoluminescence excitation (PLE) below the resonant energies of nitrogen vacancy (NV) centers in diamond. The quadratic and cubic dependence of the integrated fluorescence intensity as a function of excitation power indicates a two-photon excitation pathway for the NV- charge state and a three-photon process involved for the neutral NV0 charge state, respectively. Comparing the total multiphoton energy with its single-photon equivalent, the PLE spectra follows the absorption spectrum of single photon excitation. We also observed that the efficiency of photoluminescence for different charge states, as well as the decay time constant, was dependent on the excitation wavelength and power.

Quantum-Dot Single-Photon Sources for Entanglement Enhanced Interferometry.

PubMed

Müller, M; Vural, H; Schneider, C; Rastelli, A; Schmidt, O G; Höfling, S; Michler, P

2017-06-23

Multiphoton entangled states such as "N00N states" have attracted a lot of attention because of their possible application in high-precision, quantum enhanced phase determination. So far, N00N states have been generated in spontaneous parametric down-conversion processes and by mixing quantum and classical light on a beam splitter. Here, in contrast, we demonstrate superresolving phase measurements based on two-photon N00N states generated by quantum dot single-photon sources making use of the Hong-Ou-Mandel effect on a beam splitter. By means of pulsed resonance fluorescence of a charged exciton state, we achieve, in postselection, a quantum enhanced improvement of the precision in phase uncertainty, higher than prescribed by the standard quantum limit. An analytical description of the measurement scheme is provided, reflecting requirements, capability, and restraints of single-photon emitters in optical quantum metrology. Our results point toward the realization of a real-world quantum sensor in the near future.

Atom-Dependent Edge-Enhanced Second-Harmonic Generation on MoS2 Monolayers.

PubMed

Lin, Kuang-I; Ho, Yen-Hung; Liu, Shu-Bai; Ciou, Jian-Jhih; Huang, Bo-Ting; Chen, Christopher; Chang, Han-Ching; Tu, Chien-Liang; Chen, Chang-Hsiao

2018-02-14

Edge morphology and lattice orientation of single-crystal molybdenum disulfide (MoS 2 ) monolayers, a transition metal dichalcogenide (TMD), possessing a triangular shape with different edges grown by chemical vapor deposition are characterized by atomic force microscopy and transmission electron microscopy. Multiphoton laser scanning microscopy is utilized to study one-dimensional atomic edges of MoS 2 monolayers with localized midgap electronic states, which result in greatly enhanced optical second-harmonic generation (SHG). Microscopic S-zigzag edge and S-Mo Klein edge (bare Mo atoms protruding from a S-zigzag edge) terminations and the edge-atom dependent resonance energies can therefore be deduced based on SHG images. Theoretical calculations based on density functional theory clearly explain the lower energy of the S-zigzag edge states compared to the corresponding S-Mo Klein edge states. Characterization of the atomic-scale variation of edge-enhanced SHG is a step forward in this full-optical and high-yield technique of atomic-layer TMDs.

Ionizing radiation changes the electronic properties of melanin and enhances the growth of melanized fungi.

PubMed

Dadachova, Ekaterina; Bryan, Ruth A; Huang, Xianchun; Moadel, Tiffany; Schweitzer, Andrew D; Aisen, Philip; Nosanchuk, Joshua D; Casadevall, Arturo

2007-05-23

Melanin pigments are ubiquitous in nature. Melanized microorganisms are often the dominating species in certain extreme environments, such as soils contaminated with radionuclides, suggesting that the presence of melanin is beneficial in their life cycle. We hypothesized that ionizing radiation could change the electronic properties of melanin and might enhance the growth of melanized microorganisms. Ionizing irradiation changed the electron spin resonance (ESR) signal of melanin, consistent with changes in electronic structure. Irradiated melanin manifested a 4-fold increase in its capacity to reduce NADH relative to non-irradiated melanin. HPLC analysis of melanin from fungi grown on different substrates revealed chemical complexity, dependence of melanin composition on the growth substrate and possible influence of melanin composition on its interaction with ionizing radiation. XTT/MTT assays showed increased metabolic activity of melanized C. neoformans cells relative to non-melanized cells, and exposure to ionizing radiation enhanced the electron-transfer properties of melanin in melanized cells. Melanized Wangiella dermatitidis and Cryptococcus neoformans cells exposed to ionizing radiation approximately 500 times higher than background grew significantly faster as indicated by higher CFUs, more dry weight biomass and 3-fold greater incorporation of (14)C-acetate than non-irradiated melanized cells or irradiated albino mutants. In addition, radiation enhanced the growth of melanized Cladosporium sphaerospermum cells under limited nutrients conditions. Exposure of melanin to ionizing radiation, and possibly other forms of electromagnetic radiation, changes its electronic properties. Melanized fungal cells manifested increased growth relative to non-melanized cells after exposure to ionizing radiation, raising intriguing questions about a potential role for melanin in energy capture and utilization.

Photofragment slice imaging studies of pyrrole and the Xe…pyrrole cluster

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

Rubio-Lago, L.; Zaouris, D.; Sakellariou, Y.

The photolysis of pyrrole has been studied in a molecular beam at wavelengths 250 nm, 240 nm and 193.3 nm, using 2 different carrier gases, He and Xe. A broad bimodal distribution of H atom fragment velocities has been observed at all wavelengths. Near threshold at both 240 and 250 nm, , sharp features have been observed in the fast part of the H-atom distribution. Under appropriate molecular beam conditions, these sharp features and the photolysis of pyrrole at both 240 and 250 nm disappear when using Xe as opposed to He as the carrier gas. We attribute this phenomenonmore » to cluster formation between Xe and pyrrole, and this assumption is supported by observation of resonance enhanced multiphoton ionization spectra for the (Xe…pyrrole) cluster followed by photofragmentation of the nascent cation cluster. Ab initio calculations are performed to support the experimental data. Part of this work is supported by the transfer of knowledge program SOUTHERN DYNAMICS MTKD-CT-2004-014306. The experimental work was performed at the Ultraviolet Laser Facility operating at IESL-FORTH and has been supported in part by the European Commission through the Research Infrastructures activity of FP6 (“Laserlab- Europe” RII3-CT-2003-506350). We also wish to thank the graduate program Applied Molecular Spectroscopy (EPEAEK). Part of this work was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, US Department of Energy with Battelle Memorial Institute, which operates the Pacific Northwest National Laboratory. Computer resources were provided by the Office of Science, US Department of Energy.« less

Watching proton transfer in real time: Ultrafast photoionization-induced proton transfer in phenol-ammonia complex cation.

PubMed

Shen, Ching-Chi; Tsai, Tsung-Ting; Wu, Jun-Yi; Ho, Jr-Wei; Chen, Yi-Wei; Cheng, Po-Yuan

2017-10-28

In this paper, we give a full account of our previous work [C. C. Shen et al., J. Chem. Phys. 141, 171103 (2014)] on the study of an ultrafast photoionization-induced proton transfer (PT) reaction in the phenol-ammonia (PhOH-NH 3 ) complex using ultrafast time-resolved ion photofragmentation spectroscopy implemented by the photoionization-photofragmentation pump-probe detection scheme. Neutral PhOH-NH 3 complexes prepared in a free jet are photoionized by femtosecond 1 + 1 resonance-enhanced multiphoton ionization via the S 1 state. The evolving cations are then probed by delayed pulses that result in ion fragmentation, and the ionic dynamics is followed by measuring the parent-ion depletion as a function of the pump-probe delay time. By comparing with systems in which PT is not feasible and the steady-state ion photofragmentation spectra, we concluded that the observed temporal evolutions of the transient ion photofragmentation spectra are consistent with an intracomplex PT reaction after photoionization from the initial non-PT to the final PT structures. Our experiments revealed that PT in [PhOH-NH 3 ] + cation proceeds in two distinct steps: an initial impulsive wave-packet motion in ∼70 fs followed by a slower relaxation of about 1 ps that stabilizes the system into the final PT configuration. These results indicate that for a barrierless PT system, even though the initial PT motions are impulsive and ultrafast, the time scale to complete the reaction can be much slower and is determined by the rate of energy dissipation into other modes.

Photodissociation of cis-, trans-, and 1,1-dichloroethylene in the ultraviolet range: characterization of Cl((2)P(J)) elimination.

PubMed

Hua, Linqiang; Zhang, Xiaopeng; Lee, Wei-Bin; Chao, Meng-Hsuan; Zhang, Bing; Lin, King-Chuen

2010-01-14

By using photofragment velocity imaging detection coupled with a (2 + 1) resonance-enhanced multiphoton ionization technique, the elimination channel of spin-orbit chlorine atoms in photodissociation of cis-, trans-, and 1,1-dichloroethylene at two photolysis wavelengths of 214.5 and 235 nm is investigated. Translational energy and angular distributions of Cl((2)P(J)) fragmentation are acquired. The Cl((2)P(J)) fragments are produced by two competing channels. The fast dissociation component with higher translational energy is characterized by a Gaussian distribution, resulting from a curve crossing of the initially excited (pi, pi*) state to nearby repulsive (pi, sigma*) and/or (n, sigma*). In contrast, the slow component with a lower translational energy is characterized by a Boltzmann distribution, which dissociates on the vibrationally hot ground state relaxed from the (pi, pi*) state via internal conversion. cis-C(2)H(2)Cl(2) is found to have a larger branching of Boltzmann component than the other two isomers. The fraction of available energy partitioning into translation increases along the trend of cis- < trans- < 1,1-C(2)H(2)Cl(2). This trend may be fitted by a rigid radical model and interpreted by means of a torque generated during the C-Cl bond cleavage. The anisotropy parameters are determined, and the transition dipole moments are expected to be essentially along the C horizontal lineC bond axis. The results are also predicted theoretically. The relative quantum yields of Cl((2)P(J)) have a similar value for the three isomers at the two photolysis wavelengths.

Overview: MURI Center on spectroscopic and time domain detection of trace explosives in condensed and vapor phases

NASA Astrophysics Data System (ADS)

Spicer, James B.; Dagdigian, Paul; Osiander, Robert; Miragliotta, Joseph A.; Zhang, Xi-Cheng; Kersting, Roland; Crosley, David R.; Hanson, Ronald K.; Jeffries, Jay

2003-09-01

The research center established by Army Research Office under the Multidisciplinary University Research Initiative program pursues a multidisciplinary approach to investigate and advance the use of complementary analytical techniques for sensing of explosives and/or explosive-related compounds as they occur in the environment. The techniques being investigated include Terahertz (THz) imaging and spectroscopy, Laser-Induced Breakdown Spectroscopy (LIBS), Cavity Ring Down Spectroscopy (CRDS) and Resonance Enhanced Multiphoton Ionization (REMPI). This suite of techniques encompasses a diversity of sensing approaches that can be applied to detection of explosives in condensed phases such as adsorbed species in soil or can be used for vapor phase detection above the source. Some techniques allow for remote detection while others have highly specific and sensitive analysis capabilities. This program is addressing a range of fundamental, technical issues associated with trace detection of explosive related compounds using these techniques. For example, while both LIBS and THz can be used to carry-out remote analysis of condensed phase analyte from a distance in excess several meters, the sensitivities of these techniques to surface adsorbed explosive-related compounds are not currently known. In current implementations, both CRDS and REMPI require sample collection techniques that have not been optimized for environmental applications. Early program elements will pursue the fundamental advances required for these techniques including signature identification for explosive-related compounds/interferents and trace analyte extraction. Later program tasks will explore simultaneous application of two or more techniques to assess the benefits of sensor fusion.

Watching proton transfer in real time: Ultrafast photoionization-induced proton transfer in phenol-ammonia complex cation

NASA Astrophysics Data System (ADS)

Shen, Ching-Chi; Tsai, Tsung-Ting; Wu, Jun-Yi; Ho-Wei, Jr.; Chen, Yi-Wei; Cheng, Po-Yuan

2017-10-01

In this paper, we give a full account of our previous work [C. C. Shen et al., J. Chem. Phys. 141, 171103 (2014)] on the study of an ultrafast photoionization-induced proton transfer (PT) reaction in the phenol-ammonia (PhOH-NH3) complex using ultrafast time-resolved ion photofragmentation spectroscopy implemented by the photoionization-photofragmentation pump-probe detection scheme. Neutral PhOH-NH3 complexes prepared in a free jet are photoionized by femtosecond 1 + 1 resonance-enhanced multiphoton ionization via the S1 state. The evolving cations are then probed by delayed pulses that result in ion fragmentation, and the ionic dynamics is followed by measuring the parent-ion depletion as a function of the pump-probe delay time. By comparing with systems in which PT is not feasible and the steady-state ion photofragmentation spectra, we concluded that the observed temporal evolutions of the transient ion photofragmentation spectra are consistent with an intracomplex PT reaction after photoionization from the initial non-PT to the final PT structures. Our experiments revealed that PT in [PhOH-NH3]+ cation proceeds in two distinct steps: an initial impulsive wave-packet motion in ˜70 fs followed by a slower relaxation of about 1 ps that stabilizes the system into the final PT configuration. These results indicate that for a barrierless PT system, even though the initial PT motions are impulsive and ultrafast, the time scale to complete the reaction can be much slower and is determined by the rate of energy dissipation into other modes.

Preparation of Vibrationally Excited H2 in a Coherent Superposition of M-States Using Stark Induced Adiabatic Raman Passage (SARP)

NASA Astrophysics Data System (ADS)

Mukherjee, Nandini; Dong, Wenrui; Perreault, William; Zare, Richard

2017-04-01

We prepare a large ensemble of rovibrationally excited (v = 1, J = 2) H2 molecules in a coherent superposition of M-states using Stark-induced adiabatic Raman passage (SARP) with linearly polarized single mode pump (532 nm) and Stokes (699 nm) laser pulses of duration 6 ns and 4 ns. A biaxial superposition state, | ψ〉 = 1/ √2 [ | v = 1, J = 2, M = -2〉- | v = 1, J = 2, M = + 2〉], is prepared using SARP with a sequence of a pump laser pulse partially overlapping with a cross polarized Stokes laser pulse co-propagating along the quantization z-axis. The degree of phase coherence is measured by recording interference fringes in the ion signal produced using the O(2) line of 2 +1 resonance enhanced multiphoton ionization (REMPI) from the rovibrationally excited (v = 1, J = 2) level as a function of REMPI laser polarization angle. The ion signal is measured using a time-of-flight mass spectrometer. Nearly 60% population transfer from H2 (v = 0, J = 0) ground state to the superposition state in H2 (v = 1, J = 2) is measured from the depletion of Q(0) REMPI signal of the (v = 0, J = 0) ground state. The M-state superposition behaves much like a multi-slit interferometer where the number of slits, i.e. the number of M-states, and their separations, i.e. the relative phase, can be varied experimentally. This work has been supported by the U.S. Army Research Office.

Platinum Acetylide Two-Photon Chromophores (Preprint)

DTIC Science & Technology

2007-04-01

nonlinear photonics,6-s microfabrication,9,10 fluorescence imaging, II and photodynamic therapy.12Instantaneous absorption of two lower energy photons...results in initiation of the same photophysical processes as one-photon absorption (lP A) of one high- energy photon. This is advantageous for two...reasons. The first is that because of the use of a lower energy photon a material will be guarded from ionization effects from multiphoton absorption in

Improvement of depth resolution on photoacoustic imaging using multiphoton absorption

NASA Astrophysics Data System (ADS)

Yamaoka, Yoshihisa; Fujiwara, Katsuji; Takamatsu, Tetsuro

2007-07-01

Commercial imaging systems, such as computed tomography and magnetic resonance imaging, are frequently used powerful tools for observing structures deep within the human body. However, they cannot precisely visualized several-tens micrometer-sized structures for lack of spatial resolution. In this presentation, we propose photoacoustic imaging using multiphoton absorption technique to generate ultrasonic waves as a means of improving depth resolution. Since the multiphoton absorption occurs at only the focus point and the employed infrared pulses deeply penetrate living tissues, it enables us to extract characteristic features of structures embedded in the living tissue. When nanosecond pulses from a 1064-nm Nd:YAG laser were focused on Rhodamine B/chloroform solution (absorption peak: 540 nm), the peak intensity of the generated photoacoustic signal was proportional to the square of the input pulse energy. This result shows that the photoacoustic signals can be induced by the two-photon absorption of infrared nanosecond pulse laser and also can be detected by a commercial low-frequency MHz transducer. Furthermore, in order to evaluate the depth resolution of multiphoton-photoacoustic imaging, we investigated the dependence of photoacoustic signal on depth position using a 1-mm-thick phantom in a water bath. We found that the depth resolution of two-photon photoacoustic imaging (1064 nm) is greater than that of one-photon photoacoustic imaging (532 nm). We conclude that evolving multiphoton-photoacoustic imaging technology renders feasible the investigation of biomedical phenomena at the deep layer in living tissue.

Application of parametric equations of motion to study the laser induced multiphoton dissociation of H2+ in intense laser field.

PubMed

Kalita, Dhruba J; Rao, Akshay; Rajvanshi, Ishir; Gupta, Ashish K

2011-06-14

We have applied parametric equations of motion (PEM) to study photodissociation dynamics of H(2)(+). The resonances are extracted using smooth exterior scaling method. This is the first application of PEM to non-Hermitian Hamiltonian that includes resonances and the continuum. Here, we have studied how the different resonance states behave with respect to the change in field amplitude. The advantage of this method is that one can easily trace the different states that are changing as the field parameter changes.

UV + V UV double-resonance studies of autoionizing Rydberg states of the hydroxyl radical

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

Green, Amy M.; Liu, Fang; Lester, Marsha I., E-mail: milester@sas.upenn.edu

2016-05-14

The hydroxyl radical (OH) is a key oxidant in atmospheric and combustion chemistry. Recently, a sensitive and state-selective ionization method has been developed for detection of the OH radical that utilizes UV excitation on the A{sup 2}Σ{sup +}–X{sup 2}Π transition followed by fixed 118 nm vacuum ultraviolet (VUV) radiation to access autoionizing Rydberg states [J. M. Beames et al., J. Chem. Phys. 134, 241102 (2011)]. The present study uses tunable VUV radiation generated by four-wave mixing to examine the origin of the enhanced ionization efficiency observed for OH radicals prepared in specific A{sup 2}Σ{sup +} intermediate levels. The enhancement ismore » shown to arise from resonant excitation to distinct rotational and fine structure levels of two newly identified {sup 2}Π Rydberg states with an A{sup 3}Π cationic core and a 3d electron followed by ionization. Spectroscopic constants are derived and effects due to uncoupling of the Rydberg electron are revealed for the OH {sup 2}Π Rydberg states. The linewidths indicate a Rydberg state lifetime due to autoionization on the order of a picosecond.« less

Optimal control of multiphoton ionization dynamics of small alkali aggregates

NASA Astrophysics Data System (ADS)

Lindinger, A.; Bartelt, A.; Lupulescu, C.; Vajda, S.; Woste, Ludger

2003-11-01

We have performed transient multi-photon ionization experiments on small alkali clusters of different size in order to probe their wave packet dynamics, structural reorientations, charge transfers and dissociative events in different vibrationally excited electronic states including their ground state. The observed processes were highly dependent on the irradiated pulse parameters like wavelength range or its phase and amplitude; an emphasis to employ a feedback control system for generating the optimum pulse shapes. Their spectral and temporal behavior reflects interesting properties about the investigated system and the irradiated photo-chemical process. First, we present the vibrational dynamics of bound electronically excited states of alkali dimers and trimers. The scheme for observing the wave packet dynamics in the electronic ground state using stimulated Raman-pumping is shown. Since the employed pulse parameters significantly influence the efficiency of the irradiated dynamic pathways photo-induced ioniziation experiments were carried out. The controllability of 3-photon ionization pathways is investigated on the model-like systems NaK and K2. A closed learning loop for adaptive feedback control is used to find the optimal fs pulse shape. Sinusoidal parameterizations of the spectral phase modulation are investigated in regard to the obtained optimal field. By reducing the number of parameters and thereby the complexity of the phase moduation, optimal pulse shapes can be generated that carry fingerprints of the molecule's dynamical properties. This enables to find "understandable" optimal pulse forms and offers the possiblity to gain insight into the photo-induced control process. Characteristic motions of the involved wave packets are proposed to explain the optimized dynamic dissociation pathways.

Clocking Femtosecond Collisional Dynamics via Resonant X-Ray Spectroscopy

NASA Astrophysics Data System (ADS)

van den Berg, Q. Y.; Fernandez-Tello, E. V.; Burian, T.; Chalupský, J.; Chung, H.-K.; Ciricosta, O.; Dakovski, G. L.; Hájková, V.; Hollebon, P.; Juha, L.; Krzywinski, J.; Lee, R. W.; Minitti, M. P.; Preston, T. R.; de la Varga, A. G.; Vozda, V.; Zastrau, U.; Wark, J. S.; Velarde, P.; Vinko, S. M.

2018-02-01

Electron-ion collisional dynamics is of fundamental importance in determining plasma transport properties, nonequilibrium plasma evolution, and electron damage in diffraction imaging applications using bright x-ray free-electron lasers (FELs). Here we describe the first experimental measurements of ultrafast electron impact collisional ionization dynamics using resonant core-hole spectroscopy in a solid-density magnesium plasma, created and diagnosed with the Linac Coherent Light Source x-ray FEL. By resonantly pumping the 1 s →2 p transition in highly charged ions within an optically thin plasma, we have measured how off-resonance charge states are populated via collisional processes on femtosecond time scales. We present a collisional cross section model that matches our results and demonstrates how the cross sections are enhanced by dense-plasma effects including continuum lowering. Nonlocal thermodynamic equilibrium collisional radiative simulations show excellent agreement with the experimental results and provide new insight on collisional ionization and three-body-recombination processes in the dense-plasma regime.

Clocking Femtosecond Collisional Dynamics via Resonant X-Ray Spectroscopy

DOE PAGES

van den Berg, Q. Y.; Fernandez-Tello, E. V.; Burian, T.; ...

2018-02-01

Electron-ion collisional dynamics is of fundamental importance in determining plasma transport properties, nonequilibrium plasma evolution, and electron damage in diffraction imaging applications using bright x-ray free-electron lasers (FELs). Here in this paper, we describe the first experimental measurements of ultrafast electron impact collisional ionization dynamics using resonant core-hole spectroscopy in a solid-density magnesium plasma, created and diagnosed with the Linac Coherent Light Source x-ray FEL. By resonantly pumping the 1s → 2p transition in highly charged ions within an optically thin plasma, we have measured how off-resonance charge states are populated via collisional processes on femtosecond time scales. We presentmore » a collisional cross section model that matches our results and demonstrates how the cross sections are enhanced by dense-plasma effects including continuum lowering. Nonlocal thermodynamic equilibrium collisional radiative simulations show excellent agreement with the experimental results and provide new insight on collisional ionization and three-body-recombination processes in the dense-plasma regime.« less

Confluence or independence of microwave plasma bullets in atmospheric argon plasma jet plumes

NASA Astrophysics Data System (ADS)

Li, Ping; Chen, Zhaoquan; Mu, Haibao; Xu, Guimin; Yao, Congwei; Sun, Anbang; Zhou, Yuming; Zhang, Guanjun

2018-03-01

Plasma bullet is the formation and propagation of a guided ionization wave (streamer), normally generated in atmospheric pressure plasma jet (APPJ). In most cases, only an ionization front produces in a dielectric tube. The present study shows that two or three ionization fronts can be generated in a single quartz tube by using a microwave coaxial resonator. The argon APPJ plumes with a maximum length of 170 mm can be driven by continuous microwaves or microwave pulses. When the input power is higher than 90 W, two or three ionization fronts propagate independently at first; thereafter, they confluence to form a central plasma jet plume. On the other hand, the plasma bullets move independently as the lower input power is applied. For pulsed microwave discharges, the discharge images captured by a fast camera show the ionization process in detail. Another interesting finding is that the strongest lightening plasma jet plumes always appear at the shrinking phase. Both the discharge images and electromagnetic simulations suggest that the confluence or independent propagation of plasma bullets is resonantly excited by the local enhanced electric fields, in terms of wave modes of traveling surface plasmon polaritons.

HF-enhanced 4278-Å airglow: evidence of accelerated ionosphere electrons?

NASA Astrophysics Data System (ADS)

Fallen, C. T.; Watkins, B. J.

2013-12-01

We report calculations from a one-dimensional physics-based self-consistent ionosphere model (SCIM) demonstrating that HF-heating of F-region electrons can produce 4278-Å airglow enhancements comparable in magnitude to those reported during ionosphere HF modification experiments at the High-frequency Active Auroral Research Program (HAARP) observatory in Alaska. These artificial 'blue-line' emissions, also observed at the EISCAT ionosphere heating facility in Norway, have been attributed to arise solely from additional production of N2+ ions through impact ionization of N2 molecules by HF-accelerated electrons. Each N2+ ion produced by impact ionization or photoionization has a probability of being created in the N2+(1N) excited state, resulting in a blue-line emission from the allowed transition to its ground state. The ionization potential of N2 exceeds 18 eV, so enhanced impact ionization of N2 implies that significant electron acceleration processes occur in the HF-modified ionosphere. Further, because of the fast N2+ emission time, measurements of 4278-Å intensity during ionosphere HF modification experiments at HAARP have also been used to estimate artificial ionization rates. To the best of our knowledge, all observations of HF-enhanced blue-line emissions have been made during twilight conditions when resonant scattering of sunlight by N2+ ions is a significant source of 4278-Å airglow. Our model calculations show that F-region electron heating by powerful O-mode HF waves transmitted from HAARP is sufficient to increase N2+ ion densities above the shadow height through temperature-enhanced ambipolar diffusion and temperature-suppressed ion recombination. Resonant scattering from the modified sunlit region can cause a 10-20 R increase in 4278-Å airglow intensity, comparable in magnitude to artificial emissions measured during ionosphere HF-modification experiments. This thermally-induced artificial 4278-Å aurora occurs independently of any artificial aurora maintained by HF-accelerated (non-thermal) electrons. The numerical results presented here do not necessarily rule out the presence of HF-accelerated electrons with energies exceeding 18 eV. However, vertical or field-aligned airglow intensity measurements made during twilight conditions do not provide definitive evidence of energetic HF-accelerated electrons. Consequently, artificial blue-line airglow measurements should not be used to estimate N2+ ionization rates without also accounting for temperature-dependent chemistry and diffusion. Future experiments that make simultaneous measurements of N2+ ion airglow emissions from both the first negative bands and the Meinel bands can potentially resolve the relative contributions of accelerated electron and resonant scattering mechanisms. Airglow emission rates from these bands are expected to be in strict proportion when the emissions result from electron impact ionization of N2 molecules. Side-view altitude-resolved 4278-Å airglow measurements may also indicate the presence of energetic HF-accelerated electrons if the blue-line emissions are determined to occur below the shadow height.

Sequential and direct ionic excitation in the strong-field ionization of 1-butene molecules.

PubMed

Schell, Felix; Boguslavskiy, Andrey E; Schulz, Claus Peter; Patchkovskii, Serguei; Vrakking, Marc J J; Stolow, Albert; Mikosch, Jochen

2018-05-18

We study the Strong-Field Ionization (SFI) of the hydrocarbon 1-butene as a function of wavelength using photoion-photoelectron covariance and coincidence spectroscopy. We observe a striking transition in the fragment-associated photoelectron spectra: from a single Above Threshold Ionization (ATI) progression for photon energies less than the cation D0-D1 gap to two ATI progressions for a photon energy greater than this gap. For the first case, electronically excited cations are created by SFI populating the ground cationic state D0, followed by sequential post-ionization excitation. For the second case, direct sub-cycle SFI to the D1 excited cation state contributes significantly. Our experiments access ionization dynamics in a regime where strong-field and resonance-enhanced processes can interplay.

Which role does multiphoton interference play in small phase estimation in quantum Fourier transform interferometers?

NASA Astrophysics Data System (ADS)

Zimmermann, Olaf; Tamma, Vincenzo

Recently, quantum Fourier transform interferometers have been demonstrated to allow a quantum metrological enhancement in phase sensitivity for a small number n of identical input single photons [J. P. Olson, K. R. Motes, P. M. Birchall, N. M. Studer, M. LaBorde, T. Moulder, P. P. Rohde and J. P. Dowling, Phys. Rev. A 96 (2017) 013810; K. R. Motes, J. P. Olson, E. J. Rabeaux, J. P. Dowling, S. J. Olson and P. P. Rohde, Phys. Rev. Lett. 114 (2015) 170802; O. Zimmermann, Bachelor Thesis (Ulm University, 2015) arXiv: 1710.03805.]. However, multiphoton distinguishability at the detectors can play an important role from an experimental point of view [V. Tamma and S. Laibacher, Phys. Rev. Lett. 114 (2015) 243601.]. This raises a fundamental question: How is the phase sensitivity affected when the photons are completely distinguishable at the detectors and therefore do not interfere? In other words, which role does multiphoton interference play in these schemes? Here, we show that for small phase values, the phase sensitivity achievable in the proposed schemes with indistinguishable photons is enhanced only by a constant factor with respect to the case of completely distinguishable photons at the detectors. Interestingly, this enhancement arises from the interference of only a polynomial number (in n) of the total n! multiphoton path amplitudes in the n-port interferometer. These results are independent of the number n of single photons and of the phase weight factors employed at each interferometer channel.

Characterization of a Continuous Wave Laser for Resonance Ionization Mass Spectroscopy Analysis in Nuclear Forensics

DTIC Science & Technology

2015-06-01

OF A CONTINUOUS WAVE LASER FOR RESONANCE IONIZATION MASS SPECTROSCOPY ANALYSIS IN NUCLEAR FORENSICS by Sunny G. Lau June 2015 Thesis...IONIZATION MASS SPECTROSCOPY ANALYSIS IN NUCLEAR FORENSICS 5. FUNDING NUMBERS 6. AUTHOR(S) Sunny G. Lau 7. PERFORMING ORGANIZATION NAME(S) AND...200 words) The application of resonance ionization mass spectroscopy (RIMS) to nuclear forensics involves the use of lasers to selectively ionize

Ionizing Radiation Changes the Electronic Properties of Melanin and Enhances the Growth of Melanized Fungi

PubMed Central

Dadachova, Ekaterina; Bryan, Ruth A.; Huang, Xianchun; Moadel, Tiffany; Schweitzer, Andrew D.; Aisen, Philip; Nosanchuk, Joshua D.; Casadevall, Arturo

2007-01-01

Background Melanin pigments are ubiquitous in nature. Melanized microorganisms are often the dominating species in certain extreme environments, such as soils contaminated with radionuclides, suggesting that the presence of melanin is beneficial in their life cycle. We hypothesized that ionizing radiation could change the electronic properties of melanin and might enhance the growth of melanized microorganisms. Methodology/Principal Findings Ionizing irradiation changed the electron spin resonance (ESR) signal of melanin, consistent with changes in electronic structure. Irradiated melanin manifested a 4-fold increase in its capacity to reduce NADH relative to non-irradiated melanin. HPLC analysis of melanin from fungi grown on different substrates revealed chemical complexity, dependence of melanin composition on the growth substrate and possible influence of melanin composition on its interaction with ionizing radiation. XTT/MTT assays showed increased metabolic activity of melanized C. neoformans cells relative to non-melanized cells, and exposure to ionizing radiation enhanced the electron-transfer properties of melanin in melanized cells. Melanized Wangiella dermatitidis and Cryptococcus neoformans cells exposed to ionizing radiation approximately 500 times higher than background grew significantly faster as indicated by higher CFUs, more dry weight biomass and 3-fold greater incorporation of 14C-acetate than non-irradiated melanized cells or irradiated albino mutants. In addition, radiation enhanced the growth of melanized Cladosporium sphaerospermum cells under limited nutrients conditions. Conclusions/Significance Exposure of melanin to ionizing radiation, and possibly other forms of electromagnetic radiation, changes its electronic properties. Melanized fungal cells manifested increased growth relative to non-melanized cells after exposure to ionizing radiation, raising intriguing questions about a potential role for melanin in energy capture and utilization. PMID:17520016

Real-time detection of hazardous materials in air

NASA Astrophysics Data System (ADS)

Schechter, Israel; Schroeder, Hartmut; Kompa, Karl L.

1994-03-01

A new detection system has been developed for real-time analysis of organic compounds in ambient air. It is based on multiphoton ionization by an unfocused laser beam in a single parallel-plate device. Thus, the ionization volume can be relatively large. The amount of laser created ions is determined quantitatively from the induced total voltage drop between the biased plates (Q equals (Delta) V(DOT)C). Mass information is obtained from computer analysis of the time-dependent signal. When a KrF laser (5 ev) is used, most of the organic compounds can be ionized in a two-photon process, but none of the standard components of atmospheric air are ionized by this process. Therefore, this instrument may be developed as a `sniffer' for organic materials. The method has been applied for benzene analysis in air. The detection limit is about 10 ppb. With a simple preconcentration technique the detection limit can be decreased to the sub-ppb range. Simple binary mixtures are also resolved.

Laser resonance ionization spectroscopy of antimony

NASA Astrophysics Data System (ADS)

Li, R.; Lassen, J.; Ruczkowski, J.; Teigelhöfer, A.; Bricault, P.

2017-02-01

The resonant ionization laser ion source is an element selective, efficient and versatile ion source to generate radioactive ion beams at on-line mass separator facilities. For some elements with complex atomic structures and incomplete spectroscopic data, laser spectroscopic investigations are required for ionization scheme development. Laser resonance ionization spectroscopy using Ti:Sa lasers has been performed on antimony (Sb) at TRIUMF's off-line laser ion source test stand. Laser light of 230.217 nm (vacuum wavelength) as the first excitation step and light from a frequency-doubled Nd:YVO4 laser (532 nm) as the nonresonant ionization step allowed to search for suitable second excitation steps by continuous wavelength scans from 720 nm to 920 nm across the wavelength tuning range of a grating-tuned Ti:Sa laser. Upon the identification of efficient SES, the third excitation steps for resonance ionization were investigated by laser scans across Rydberg states, the ionization potential and autoionizing states. One Rydberg state and six AI states were found to be well suitable for efficient resonance ionization.

Multiphoton microscopy and image guided light activated therapy using nanomaterials (Conference Presentation)

NASA Astrophysics Data System (ADS)

Prasad, Paras N.

2017-02-01

This talk will focus on design and applications of nanomaterials exhibiting strong multiphoton upconversion for multiphoton microscopy as well as for image-guided and light activated therapy .1-3 Such processes can occur by truly nonlinear optical interactions proceeding through virtual intermediate states or by stepwise coupled linear excitations through real intermediate states. Multiphoton processes in biocompatible multifunctional nanoparticles allow for 3D deep tissue imaging. In addition, they can produce in-situ photon conversion of deep tissue penetrating near IR light into a needed shorter wavelength light for photo-activated therapy at a targeted site, thus overcoming the limited penetration of UV or visible light into biological media. We are using near IR emitters such as silicon quantum dots which also exhibit strong multiphoton excitation for multiphoton microscopy. Another approach involves nonlinear nanocrystals such as ZnO which can produce four wave mixing, sum frequency generation as well as second harmonic generation to convert a deep tissue penetrating Near IR light at the targeted biological site to a desired shorter wavelength light suitable for bio imaging or activation of a therapy. We have utilized this approach to activate a photosensitizer for photodynamic therapy. Yet another type of upconversion materials is rare-earth ion doped optical nanotransformers which transform a Near IR (NIR) light from an external source by sequential single photon absorption, in situ and on demand, to a needed wavelength. Applications of these nanotransformers in multiphoton photoacoustic imaging will also be presented. An exciting direction pursued by us using these multiphoton nanoparticles, is functional imaging of brain. Simultaneously, they can effect optogenetics for regioselective stimulation of neurons for providing an effective intervention/augmentation strategy to enhance the cognitive state and lead to a foundation for futuristic vision of super human capabilities. Challenges and opportunities will be discussed.

Theoretical Studies Relating to the Interaction of Radiation with Matter

DTIC Science & Technology

1989-09-15

and Heisenberg picture calculations of resonance fluorescence in the presence of a strong field. Again, the Schrodinger calculation is quite...discussed in Sec. VIII. numerous effects have been discussed assuming fluctuat- ing radiation fields (resonant fluorescence , double reso- nance, multiphoton...tered at t12 =0. The peak has temporal width It 2 1 = rcl2 and, moreover, for fully correlated pulses (0) = 1) there is FIG. 6. Signal of order n = 1 as a

Multimodal Nonlinear Optical Microscopy

PubMed Central

Yue, Shuhua; Slipchenko, Mikhail N.; Cheng, Ji-Xin

2013-01-01

Because each nonlinear optical (NLO) imaging modality is sensitive to specific molecules or structures, multimodal NLO imaging capitalizes the potential of NLO microscopy for studies of complex biological tissues. The coupling of multiphoton fluorescence, second harmonic generation, and coherent anti-Stokes Raman scattering (CARS) has allowed investigation of a broad range of biological questions concerning lipid metabolism, cancer development, cardiovascular disease, and skin biology. Moreover, recent research shows the great potential of using CARS microscope as a platform to develop more advanced NLO modalities such as electronic-resonance-enhanced four-wave mixing, stimulated Raman scattering, and pump-probe microscopy. This article reviews the various approaches developed for realization of multimodal NLO imaging as well as developments of new NLO modalities on a CARS microscope. Applications to various aspects of biological and biomedical research are discussed. PMID:24353747

Photoelectron spectroscopy of aqueous solutions: Streaming potentials of NaX (X = Cl, Br, and I) solutions and electron binding energies of liquid water and X{sup −}

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

Kurahashi, Naoya; Horio, Takuya; Suzuki, Toshinori, E-mail: suzuki@kuchem.kyoto-u.ac.jp

2014-05-07

The streaming potentials of liquid beams of aqueous NaCl, NaBr, and NaI solutions are measured using soft X-ray, He(I), and laser multiphoton ionization photoelectron spectroscopy. Gaseous molecules are ionized in the vicinity of liquid beams and the photoelectron energy shifts are measured as a function of the distance between the ionization point and the liquid beam. The streaming potentials change their polarity with concentration of electrolytes, from which the singular points of concentration eliminating the streaming potentials are determined. The streaming currents measured in air also vanish at these concentrations. The electron binding energies of liquid water and I{sup −},more » Br{sup −}, and Cl{sup −} anions are revisited and determined more accurately than in previous studies.« less

Chemical analyses of provided samples

NASA Technical Reports Server (NTRS)

Becker, Christopher H.

1993-01-01

Two batches of samples were received and chemical analysis was performed of the surface and near surface regions of the samples by the surface analysis by laser ionization (SALI) method. The samples included four one-inch optics and several paint samples. The analyses emphasized surface contamination or modification. In these studies, pulsed sputtering by 7 keV Ar+ and primarily single-photon ionization (SPI) by coherent 118 nm radiation (at approximately 5 x 10(exp 5) W/cm(sup 2) were used. For two of the samples, also multiphoton ionization (MPI) at 266 nm (approximately 5 x 10(exp 11) W/cm(sup 2) was used. Most notable among the results was the silicone contamination on Mg2 mirror 28-92, and that the Long Duration Exposure Facility (LDEF) paint sample had been enriched in K and Na and depleted in Zn, Si, B, and organic compounds relative to the control paint.

Modeling of Plutonium Ionization Probabilities for Use in Nuclear Forensic Analysis by Resonance Ionization Mass Spectrometry

DTIC Science & Technology

2016-12-01

masses collide, they form a supercritical mass . Criticality refers to the neutron population within the system. A critical system is one that can...Spectrometry, no. 242, pp. 161–168, 2005. [9] S. Raeder, “Trace analysis of actinides in the environment by means of resonance ionization mass ...first ionization potential of actinide elements by resonance ionization mass spectrometry.” Spectrochimica Acta part B: Atomic Spectroscopy. vol. 52

Current developments with TRIUMF's titanium-sapphire laser based resonance ionization laser ion source. An overview

NASA Astrophysics Data System (ADS)

Lassen, J.; Li, R.; Raeder, S.; Zhao, X.; Dekker, T.; Heggen, H.; Kunz, P.; P. Levy, C. D.; Mostanmand, M.; Teigelhöfer, A.; Ames, F.

2017-11-01

Developments at TRIUMF's isotope separator and accelerator (ISAC) resonance ionization laser ion source (RILIS) in the past years have concentrated on increased reliability for on-line beam delivery of radioactive isotopes to experiments, as well as increasing the number of elements available through resonance ionization and searching for ionization schemes with improved efficiency. The current status of these developments is given with a list of two step laser ionization schemes implemented recently.

Far-Infrared Magneto-Optical Studies in Germanium and Indium-Antimonide at High Intensities

NASA Astrophysics Data System (ADS)

Leung, Michael

Observations of nonlinear magneto-optical phenomena occurring in p-type Germanium and n-type Indium Antimonide are reported. These include multi-photon ionization of impurity states, and a new observation, the magneto-photon ionization of impurity states, and a new observation, the magneto-photon drag effect. A novel source of far-infrared radiation has been used. This source uses a pulsed CO(,2) LASER to optically pump a super-radiant cell, generating light with intensities up to 100 KW/cm('2) and wavelengths from 66 (mu)m to 496 (mu)m in a pulse of 150 nanoseconds duration. The Germanium samples were doped with Gallium, which is a shallow acceptor with an ionization potential of 11 meV. At liquid Helium temperature virtually all charge carriers are bound to acceptor sites. However, the high intensity radiation unexpectedly ionizes the acceptors. This is demonstrated through measurements of photoconductivity, transmission and the photo-Hall Effect. This observation is unexpected because the photon energy is one-fourth the ionization potential. Rate equations describing sequential multiphoton excitations are in agreement with the experimental results. The intermediate states are postulated to be acceptor exciton band states. Studies of the photoexcited mobility at 496 (mu)m suggest that at non-saturating levels of photoexcitation, the primary scattering mechanism of hot holes in Germanium is by neutral impurities. A new magneto-optical effect, the magneto-photon drag effect, has been studied in both Germanium and Indium Antimonide. This is simply the absorption of momentum by free carriers, from an incident photon field. It has been found that the mechanism for this effect is different in the two materials. In Germanium, the effect occurs when carriers make optical transitions from the heavy hole band to the light hole band. Thus, the magneto-optical behavior depends heavily upon the band structure. On the other hand, a modified Drude model (independent electron) has been found to be reasonably successful in describing the effect in InSb. The inclusion of non-parabolicity and hot electron effects gives a consistent description of the experimental observations.

Temporal and modal characterization of DoD source air toxic emission factors: final report

EPA Science Inventory

This project tested three, real-/near real-time monitoring techniques to develop air toxic emission factors for Department of Defense (DoD) platform sources. These techniques included: resonance enhanced multi photon ionization time of flight mass spectrometry (REMPI-TOFMS) for o...

Resonantly Enhanced Betatron Hard X-rays from Ionization Injected Electrons in a Laser Plasma Accelerator

PubMed Central

Huang, K.; Li, Y. F.; Li, D. Z.; Chen, L. M.; Tao, M. Z.; Ma, Y.; Zhao, J. R.; Li, M. H.; Chen, M.; Mirzaie, M.; Hafz, N.; Sokollik, T.; Sheng, Z. M.; Zhang, J.

2016-01-01

Ultrafast betatron x-ray emission from electron oscillations in laser wakefield acceleration (LWFA) has been widely investigated as a promising source. Betatron x-rays are usually produced via self-injected electron beams, which are not controllable and are not optimized for x-ray yields. Here, we present a new method for bright hard x-ray emission via ionization injection from the K-shell electrons of nitrogen into the accelerating bucket. A total photon yield of 8 × 108/shot and 108 photons with energy greater than 110 keV is obtained. The yield is 10 times higher than that achieved with self-injection mode in helium under similar laser parameters. The simulation suggests that ionization-injected electrons are quickly accelerated to the driving laser region and are subsequently driven into betatron resonance. The present scheme enables the single-stage betatron radiation from LWFA to be extended to bright γ-ray radiation, which is beyond the capability of 3rd generation synchrotrons. PMID:27273170

Two-Step Single Particle Mass Spectrometry for On-Line Monitoring of Polycyclic Aromatic Hydrocarbons Bound to Ambient Fine Particulate Matter

NASA Astrophysics Data System (ADS)

Zimmermann, R.; Bente, M.; Sklorz, M.

2007-12-01

Polycyclic aromatic hydrocarbons (PAH) are formed as trace products in combustion processes and are emitted to the atmosphere. Larger PAH have low vapour pressure and are predominantly bound to the ambient fine particulate matter (PM). Upon inhalation, PAH show both, chronic human toxicity (i.e. many PAH are potent carcinogens) as well as acute human toxicity (i.e. inflammatory effects due to oxi-dative stress) and are discussed to be relevant for the observed health effect of ambient PM. Therefore a better understanding of the occurrence, dynamics and particle size dependence of particle bound-PAH is of great interest. On-line aerosol mass spectrometry in principle is the method of choice to investigate the size resolved changes in the chemical speciation of particles as well the status of internal vs. external mixing of chemical constituents. However the present available aerosol mass spectrometers (ATOFMS and AMS) do not allow detection of PAH from ambient air PM. In order to allow a single particle based monitoring of PAH from ambient PM a new single particle laser ionisation mass spectrometer was built and applied. The system is based on ATOFMS principle but uses a two- step photo-ionization. A tracked and sized particle firstly is laser desorbed (LD) by a IR-laser pulse (CO2-laser, λ=10.2 μm) and subsequently the released PAH are selectively ionized by an intense UV-laser pulse (ArF excimer, λ=248 nm) in a resonance enhanced multiphoton ionisation process (REMPI). The PAH-ions are detected in a time of flight mass spectrometer (TOFMS). A virtual impactor enrichment unit is used to increase the detection frequency of the ambient particles. With the current inlet system particles from about 400 nm to 10 μm are accessible. Single particle based temporal profiles of PAH containing particles ion (size distribution and PAH speciation) have been recorded in Oberschleissheim, Germany from ambient air. Furthermore profiles of relevant emission sources (e.g. gasoline and diesel engine, wood combustion) and the obtained chemical profiles were compared with the ones from the ambient PAH containing particles.

Fundamental mechanisms of laser damage of dielectric crystals by ultrashort pulse: ionization dynamics for the Keldysh model

NASA Astrophysics Data System (ADS)

Gruzdev, Vitaly

2014-12-01

Laser-induced ionization is a major process that initiates and drives the initial stages of laser-induced damage (LID) of high-quality transparent solids. The ionization and its contribution to LID are characterized in terms of the time-dependent ionization rate and conduction-band electron density. Considering femtosecond pulses of various durations (from 35 to 706 fs) and variable peak irradiances (from 0.01 to 60 TW/cm2), we use a single-rate equation to simulate time variations of conduction-band electron density and rates of the photoionization and impact ionization. The photoionization rate is evaluated with the Keldysh equation. At low irradiance, the electron density and total ionization rate demonstrate power scaling characteristic of multiphoton ionization. With the increase of irradiance, there is observed a saturation of the photoionization rate due to photoionization suppression by the Keldysh-type singularity during the increase in the number of simultaneously absorbed photons by 1. A striking result is that the saturation is followed by a stepwise transition from the ionization regime which is completely dominated by the photoionization to a regime totally dominated by the impact ionization. The transition results in the increase of the electron density by a few orders of magnitude induced by a variation of peak laser irradiance by about 15% to 20%. The physical effects that are involved are discussed.

Photoelectron resonance capture ionization-aerosol mass spectrometry of the ozonolysis products of oleic acid particles: Direct measure of higher molecular weight oxygenates

NASA Astrophysics Data System (ADS)

Zahardis, James; Lafranchi, Brian W.; Petrucci, Giuseppe A.

2005-04-01

The heterogeneous reaction of particle-phase 9-octadecenoic acid (oleic acid) and gas-phase ozone in a flow reactor was studied by photoelectron resonance capture ionization (PERCI) mass spectrometry. This soft ionization technique facilitated one of the first simultaneous, direct observations of all four of the major products predicted for this reaction: nonanal, nonanoic acid, 9-oxononanoic acid, and azelaic acid. In addition, a series of higher molecular weight oxygenated compounds were observed directly for the first time. The proposed structures are all cyclic oxygenates and contain the oxygen-oxygen moiety, including secondary ozonides and cyclic geminal diperoxides. Mechanisms for the formation of these products are proposed. The mechanisms are generally 1,3-dipolar cycloadditions that lead to five- and six-member oxygen-containing rings. The mechanisms are shown to involve short-lived Criegee intermediates reacting with aldehydes and other Criegee intermediates. Atmospheric implications of these higher molecular weight compounds are suggested and include enhancing the fatty acid medium's capacity to act as a source of radicals due to the prominence of the peroxide moiety. The low volatility coupled with the high polarity of these compounds may alter particle phase hygroscopicity that can enhance the cloud condensation nuclei properties of these particles.

Differentiation and Distributions of DNA/Cisplatin Crosslinks by Liquid Chromatography-Electrospray Ionization-Infrared Multiphoton Dissociation Mass Spectrometry

PubMed Central

Xu, Zhe; Brodbelt, Jennifer S.

2013-01-01

Liquid chromatography-electrospray ionization-infrared multiphoton dissociation (IRMPD) mass spectrometry was developed to investigate the distributions of intrastrand crosslinks formed between cisplatin and two oligodeoxynucleotides (ODNs), d(A1T2G3G4G5T6A7C8C9C10A11T12) (G3-D) and its analog d(A1T2G3G4G5T6T7C8C9C10A11T12) (G3-H), that have been reported to adopt different secondary structures in solution. Based on the formation of site-specific fragment ions upon IRMPD, two isobaric crosslink products were differentiated for each ODN. The preferential formation of G3G4 and G4G5 crosslinks was determined as a function of reaction conditions, including incubation temperature and presence of metal ions. G3-D consistently exhibited a greater preference for formation of the G4G5 crosslink compared to the G3-H ODN. The ratio of G3G4:G4G5 crosslinks increased for both G3-D and G3-H at higher incubation temperatures or when metal salts were added. Comparison of the IRMPD fragmentation patterns of the unmodified ODNs and the intramolecular platinated crosslinks indicated that backbone cleavage was significantly suppressed near the crosslink. PMID:24135806

Correlated electron-nuclear dynamics in above-threshold multiphoton ionization of asymmetric molecule.

PubMed

Wang, Zhuo; Li, Min; Zhou, Yueming; Lan, Pengfei; Lu, Peixiang

2017-02-20

The partition of the photon energy into the subsystems of molecules determines many photon-induced chemical and physical dynamics in laser-molecule interactions. The electron-nuclear energy sharing from multiphoton ionization of molecules has been used to uncover the correlated dynamics of the electron and fragments. However, most previous studies focus on symmetric molecules. Here we study the electron-nuclear energy sharing in strong-field photoionization of HeH 2+ by solving the one-dimensional time-dependent Schrödinger equation (TDSE). Compared with symmetric molecules, the joint electron-nuclear energy spectrum (JES) of HeH 2+ reveals an anomalous energy shift at certain nuclear energies, while it disappears at higher and lower nuclear energies. Through tracing the time evolution of the wavepacket of bound states, we identify that this energy shift originates from the joint effect of the Stark shift, associated with the permanent dipole, and the Autler-Townes effect due to the coupling of the 2pσ and 2sσ states in strong fields. The energy shift in the JES appears at certain nuclear distances only when both Stark effect and Autler-Townes effect play important roles. We further demonstrate that the electron-nuclei energy sharing can be controlled by varying laser intensity for asymmetric molecules, providing alternative approaches to manipulate photochemical reactions for more complex molecules.

Laser-Bioplasma Interaction: Excitation and Suppression of the Brain Waves by the Multi-photon Pulsed-operated Fiber Lasers in the Ultraviolet Range of Frequencies

NASA Astrophysics Data System (ADS)

Stefan, V. Alexander; IAPS-team Team

2017-10-01

The novel study of the laser excitation-suppression of the brain waves is proposed. It is based on the pulsed-operated multi-photon fiber-laser interaction with the brain parvalbumin (PV) neurons. The repetition frequency matches the low frequency brain waves (5-100 Hz); enabling the resonance-scanning of the wide range of the PV neurons (the generators of the brain wave activity). The tunable fiber laser frequencies are in the ultraviolet frequency range, thus enabling the monitoring of the PV neuron-DNA, within the 10s of milliseconds. In medicine, the method can be used as an ``instantaneous-on-off anesthetic.'' Supported by Nikola Tesla Labs, Stefan University.

Factorization of laser-pulse ionization probabilities in the multiphotonic regime

NASA Astrophysics Data System (ADS)

Della Picca, R.; Fiol, J.; Fainstein, P. D.

2013-09-01

We present a detailed study of the ionization probability of H and H_{2}^{+} induced by a short intense laser pulse. Starting from a Coulomb-Volkov description of the process we derive a multipole-like expansion where each term is factored into two contributions: one that accounts for the effect of the electromagnetic field on the free-electron final state and a second factor that depends only on the target structure. Such a separation may be valuable to solve complex atomic or molecular systems as well as to interpret the dynamics of the process in simpler terms. We show that the series expansion converges rapidly, and thus the inclusion of the first few terms is sufficient to produce accurate results.

Jet-resolved vibronic structure in the higher excited states of N2O - Ultraviolet three-photon absorption spectroscopy from 80,000 to 90,000/cm

NASA Technical Reports Server (NTRS)

Patsilinakou, E.; Wiedmann, R. T.; Fotakis, C.; Grant, E. R.

1989-01-01

Ionization-detected UV multiphoton absorption spectroscopy of the excited states of N2O is presented, showing Rydberg structure within 20,000/cm of the first ionization threshold. Despite evidence for strong Rydberg-continuum coupling in the form of broadened bands and Fano line-shapes, the Rydberg structure persists, with atomic-like quantum defects and vibration structure well-matched with that of the ion. In the most clearly resolved spectrum, corresponding to the 3p(delta)1Pi state, Renner-Teller and Herzberg-Teller coupling of electronic and vibrational angular momentum are revealed. It is suggested that these mixings are properties of the N2O(+)Pi ion core.

Epicyclic helical channels for parametric resonance ionization cooling

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

Johson, Rolland Paul; Derbenev, Yaroslav

Proposed next-generation muon colliders will require major technical advances to achieve rapid muon beam cooling requirements. Parametric-resonance Ionization Cooling (PIC) is proposed as the final 6D cooling stage of a high-luminosity muon collider. In PIC, a half-integer parametric resonance causes strong focusing of a muon beam at appropriately placed energy absorbers while ionization cooling limits the beam’s angular spread. Combining muon ionization cooling with parametric resonant dynamics in this way should then allow much smaller final transverse muon beam sizes than conventional ionization cooling alone. One of the PIC challenges is compensation of beam aberrations over a sufficiently wide parametermore » range while maintaining the dynamical stability with correlated behavior of the horizontal and vertical betatron motion and dispersion. We explore use of a coupling resonance to reduce the dimensionality of the problem and to shift the dynamics away from non-linear resonances. PIC simulations are presented.« less

Design and implementation of fiber-based multiphoton endoscopy with microelectromechanical systems scanning

PubMed Central

Tang, Shuo; Jung, Woonggyu; McCormick, Daniel; Xie, Tuqiang; Su, Jiangping; Ahn, Yeh-Chan; Tromberg, Bruce J.; Chen, Zhongping

2010-01-01

A multiphoton endoscopy system has been developed using a two-axis microelectromechanical systems (MEMS) mirror and double-cladding photonic crystal fiber (DCPCF). The MEMS mirror has a 2-mm-diam, 20-deg optical scanning angle, and 1.26-kHz and 780-Hz resonance frequencies on the x and y axes. The maximum number of resolvable focal spots of the MEMS scanner is 720×720 on the x and y axes, which indicates that the MEMS scanner can potentially support high-resolution multiphoton imaging. The DCPCF is compared with standard single-mode fiber and hollow-core photonic bandgap fiber on the basis of dispersion, attenuation, and coupling efficiency properties. The DCPCF has high collection efficiency, and its dispersion can be compensated by grating pairs. Three configurations of probe design are investigated, and their imaging quality and field of view are compared. A two-lens configuration with a collimation and a focusing lens provides the optimum imaging performance and packaging flexibility. The endoscope is applied to image fluorescent microspheres and bovine knee joint cartilage. PMID:19566298

Determination of Hazardous Air Pollutant Surrogates Using Resonance Enhanced Multi Photon Ionization - Time of Flight Mass Spectrometry

EPA Science Inventory

EPA?s preferred approach for regulatory emissions compliance is based upon real-time monitoring of individual hazardous air pollutants (HAPs). Real-time, continuous monitoring not only provides the most comprehensive assurance of emissions compliance, but also can serve as a pro...

Biomass pyrolysis: Thermal decomposition mechanisms of furfural and benzaldehyde

NASA Astrophysics Data System (ADS)

Vasiliou, AnGayle K.; Kim, Jong Hyun; Ormond, Thomas K.; Piech, Krzysztof M.; Urness, Kimberly N.; Scheer, Adam M.; Robichaud, David J.; Mukarakate, Calvin; Nimlos, Mark R.; Daily, John W.; Guan, Qi; Carstensen, Hans-Heinrich; Ellison, G. Barney

2013-09-01

The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 μsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.

Experimental investigation and computational modeling of hot filament diamond chemical vapor deposition

NASA Astrophysics Data System (ADS)

Zumbach, Volker; Schäfer, Jörg; Tobai, Jens; Ridder, Michael; Dreier, Thomas; Schaich, Thomas; Wolfrum, Jürgen; Ruf, Bernhard; Behrendt, Frank; Deutschman, Olaf; Warnatz, Jürgen

1997-10-01

A joint investigation has been undertaken of the gas-phase chemistry taking place in a hot-filament chemical vapor-deposition (HFCVD) process for diamond synthesis on silica surfaces by a detailed comparison of numerical modeling and experimental results. Molecular beam sampling using quadrupole mass spectroscopy and resonance-enhanced multiphoton ionization time of flight mass spectroscopy (REMPI-TOF-MS) has been used to determine absolute concentrations of stable hydrocarbons and radicals. Resulting species of a CH4/H2, a CH4/D2 (both 0.5%/99.5%) and a C2H2/H2 (0.25%/99.75%) feedgas mixture were investigated for varying filament and substrate temperatures. Spatially resolved temperature profiles at various substrate temperatures, obtained from coherent anti-Stokes Raman spectroscopy (CARS) of hydrogen, are used as input parameters for the numerical code to reproduce hydrogen atom, methyl radical, methane, acetylene, and ethylene concentration profiles in the boundary layer of the substrate. In addition, the concentration of vibrationally excited hydrogen is determined by CARS. Results reveal only qualitative agreement between measured data and simulations, concerning concentrations of stable species and radicals probed near the surface, on filament and substrate temperature dependence, respectively. Hydrogen and deuterium experiments show similar behaviour for all species. In the case of CH4 as feedgas the model describes measured concentration profiles of CH3, CH4, and C2H2 qualitatively well. Large differences between model and experiment occur for hydrogen atoms (factor of 2) and C2H4 (factor of 3). For acetylene as feedgas the model is not able to give any predictions because no conversion of C2H2 is seen in the model in contrast to the experiment.

Molecular Spectra of RbSr: Helium Droplet Assisted Preparation of a Diatomic Molecule

NASA Astrophysics Data System (ADS)

Lackner, Florian; Krois, Günter; Buchsteiner, Thomas; Pototschnig, Johann V.; Ernst, Wolfgang E.

2014-06-01

We report on the first spectroscopic investigation of the ground and excited states of RbSr. The molecules are prepared in their vibronic ground state (X^2Σ^+1/2, ν" = 0) in a sequential pickup process on the surface of helium nanodroplets, confined in a cold (0.38 K) and weakly perturbing superfluid environment. Utilizing resonance-enhanced multi-photon ionization time-of-flight (REMPI-TOF) spectroscopy and laser induced fluorescence (LIF) spectroscopy our investigations cover the spectral regime of 11500 cm-1 - 23000 cm-1. The weak interaction between molecules and helium droplets causes a broadening of the observed transitions. For spectrally resolved band systems the helium droplet isolation approach facilitates the determination of molecular constants. Our assignment is assisted by theoretical calculations of potential energy curves based on a multireference configuration interaction (MRCI) approach. Several strong transitions could be identified; the most prominent spectral feature is a vibrational resolved band system at 14000 cm-1. In contrast to the excitation spectra, dispersed fluorescence (DF) spectra are not influenced by the helium environment, because the molecules leave the droplets upon photoexcitation, revealing detailed insights into the electronic structure of the free RbSr molecule. G. Krois, J.V. Pototschnig, F. Lackner and W.E. Ernst, J. Phys. Chem. A, 117 (50), 13719-13731 (2013) C. Callegari and W. E. Ernst, Helium Droplets as Nanocryostats for Molecular Spectroscopy - from the Vacuum Ultraviolet to the Microwave Regime, in: Handbook of High-Resolution Spectroscopy, eds. M. Quack and F. Merkt, John Wiley & Sons, Chichester, (2011) P.S. Żuchowski, R. Guerout, and O. Dulieu, arXiv preprint arXiv:1402.0702 (2014) B. Pasquiou, A. Bayerle, S.M. Tzanova, S. Stellmer, J. Szczepkowski, M. Parigger, R. Grimm, and F. Schreck, Phys. Rev. A, 88 (2), 023601 (2013).

Electronic spectra and excited-state dynamics of acridine and its hydrated clusters

NASA Astrophysics Data System (ADS)

Harthcock, Colin; Zhang, Jie; Kong, Wei; Mitsui, Masaaki; Ohshima, Yasuhiro

2017-04-01

We combine results from several different experiments to investigate the photophysics of acridine (Ac) and its hydrated clusters in the gas phase. Our findings are also compared with results from condensed phase studies. Similar to measurements of Ac dissolved in hydrocarbons, the lifetime of the first electronically excited state of isolated Ac in vacuum is too short for typical resonantly enhanced multiphoton ionization (REMPI) and laser induced fluorescence (LIF) experiments, hence no signal from REMPI and LIF can be attributed to monomeric Ac. Instead, sensitized phosphorescence emission spectroscopy is more successful in revealing the electronic states of Ac. Upon clustering with water, on the other hand, the lifetimes of the excited states are substantially increased to the nanosecond scale, and with two water molecules attached to Ac, the lifetime of the hydrated cluster is essentially the same as that of Ac in aqueous solutions. Detailed REMPI and ultraviolet-ultraviolet hole-burning experiments are then performed to reveal the structural information of the hydrated clusters. Although the formation of hydrogen bonds results in energy level reversal and energy separation between the first two excited states of Ac, its effect on the internal geometry of Ac is minimal, and all clusters with 1-3 water molecules demonstrate consistent intramolecular vibrational modes. Theoretical calculations reveal just one stable structure for each cluster under supersonic molecular beam conditions. Furthermore, different from mono- and di-water clusters, tri-water clusters consist of a linear chain of three water molecules attached to Ac. Consequently, the fragmentation pattern in the REMPI spectrum of tri-water clusters seems to be dominated by water trimer elimination, since the REMPI spectrum of Ac+.W3 is largely reproduced in the Ac+ mass channel, but not in the Ac+.W1 or Ac+.W2 channel.

Structure of zirconocene complexes relevant for olefin catalysis: infrared fingerprint of the Zr(C(5)H(5))(2)(OH)(CH(3)CN)(+) cation in the gas phase.

PubMed

Lagutschenkov, Anita; Springer, Andreas; Lorenz, Ulrich Joseph; Maitre, Philippe; Dopfer, Otto

2010-02-11

Cationic zirconocene complexes are active species in Ziegler-Natta catalysis for olefin polymerization. Their structure and metal-ligand bond strength strongly influence their activity. In the present work, the infrared multiphoton dissociation (IRMPD) spectrum of mass selected Zr(C(5)H(5))(2)(OH)(CH(3)CN)(+) cations was obtained in the 300-1500 cm(-1) fingerprint range by coupling a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer equipped with an electrospray ionization (ESI) source and the infrared free electron laser (IR-FEL) at the Centre Laser Infrarouge d'Orsay (CLIO). The experimental efforts are complemented by quantum chemical calculations at the MP2 and B3LYP levels using the 6-311G* basis set. Vibrational assignments of transitions observed in the IRMPD spectra to modes of the Zr-O-H, C(5)H(5), and CH(3)CN moieties are based on comparison to calculated linear absorption spectra. Both the experimental data and the calculations provide unprecedented information about structure, metal-ligand bonding, charge distribution, and binding energy of the complex.

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

Hartmann, G.; Shevchuk, I.; Walter, P.

A non-destructive diagnostic method for the characterization of circularly polarized, ultraintense, short wavelength free-electron laser (FEL) light is presented. The recently installed Delta undulator at the LCLS (Linac Coherent Light Source) at SLAC National Accelerator Laboratory (USA) was used as showcase for this diagnostic scheme. By applying a combined two-color, multi-photon experiment with polarization control, the degree of circular polarization of the Delta undulator has been determined. Towards this goal, an oriented electronic state in the continuum was created by non-resonant ionization of the O{sub 2} 1s core shell with circularly polarized FEL pulses at hν ≃ 700 eV. Anmore » also circularly polarized, highly intense UV laser pulse with hν ≃ 3.1 eV was temporally and spatially overlapped, causing the photoelectrons to redistribute into so-called sidebands that are energetically separated by the photon energy of the UV laser. By determining the circular dichroism of these redistributed electrons using angle resolving electron spectroscopy and modeling the results with the strong-field approximation, this scheme allows to unambiguously determine the absolute degree of circular polarization of any pulsed, ultraintense XUV or X-ray laser source.« less

Circular dichroism measurements at an x-ray free-electron laser with polarization control

NASA Astrophysics Data System (ADS)

Hartmann, G.; Lindahl, A. O.; Knie, A.; Hartmann, N.; Lutman, A. A.; MacArthur, J. P.; Shevchuk, I.; Buck, J.; Galler, A.; Glownia, J. M.; Helml, W.; Huang, Z.; Kabachnik, N. M.; Kazansky, A. K.; Liu, J.; Marinelli, A.; Mazza, T.; Nuhn, H.-D.; Walter, P.; Viefhaus, J.; Meyer, M.; Moeller, S.; Coffee, R. N.; Ilchen, M.

2016-08-01

A non-destructive diagnostic method for the characterization of circularly polarized, ultraintense, short wavelength free-electron laser (FEL) light is presented. The recently installed Delta undulator at the LCLS (Linac Coherent Light Source) at SLAC National Accelerator Laboratory (USA) was used as showcase for this diagnostic scheme. By applying a combined two-color, multi-photon experiment with polarization control, the degree of circular polarization of the Delta undulator has been determined. Towards this goal, an oriented electronic state in the continuum was created by non-resonant ionization of the O2 1s core shell with circularly polarized FEL pulses at hν ≃ 700 eV. An also circularly polarized, highly intense UV laser pulse with hν ≃ 3.1 eV was temporally and spatially overlapped, causing the photoelectrons to redistribute into so-called sidebands that are energetically separated by the photon energy of the UV laser. By determining the circular dichroism of these redistributed electrons using angle resolving electron spectroscopy and modeling the results with the strong-field approximation, this scheme allows to unambiguously determine the absolute degree of circular polarization of any pulsed, ultraintense XUV or X-ray laser source.

Femtosecond response of polyatomic molecules to ultra-intense hard X-rays.

PubMed

Rudenko, A; Inhester, L; Hanasaki, K; Li, X; Robatjazi, S J; Erk, B; Boll, R; Toyota, K; Hao, Y; Vendrell, O; Bomme, C; Savelyev, E; Rudek, B; Foucar, L; Southworth, S H; Lehmann, C S; Kraessig, B; Marchenko, T; Simon, M; Ueda, K; Ferguson, K R; Bucher, M; Gorkhover, T; Carron, S; Alonso-Mori, R; Koglin, J E; Correa, J; Williams, G J; Boutet, S; Young, L; Bostedt, C; Son, S-K; Santra, R; Rolles, D

2017-06-01

X-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 10 20 watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecular system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects-an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure-the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 10 20 watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.

Femtosecond response of polyatomic molecules to ultra-intense hard X-rays

DOE PAGES

Rudenko, A.; Inhester, L.; Hanasaki, K.; ...

2017-05-31

We report x-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 10 20 watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecularmore » system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects—an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure—the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 10 20 watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Fnally, our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.« less

Femtosecond response of polyatomic molecules to ultra-intense hard X-rays

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

Rudenko, A.; Inhester, L.; Hanasaki, K.

We report x-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 10 20 watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecularmore » system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects—an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure—the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 10 20 watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Fnally, our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.« less

Observation of random lasing in gold-silica nanoshell/water solution

NASA Astrophysics Data System (ADS)

Kang, Jin U.

2006-11-01

The author reports experimental observation of resonant surface plasmon enhanced random lasing in gold-silica nanoshells in de-ionized water. The gold-silica nanoshell/water solution with concentration of 8×109particles/ml was pumped above the surface plasmon resonance frequency using 514nm argon-krypton laser. When pumping power was above the lasing threshold, sharp random lasing peaks occurred near and below the plasmon peak from 720to860nm with a lasing linewidth less than 1nm.

Liver Masses: What Physicians Need to Know About Ordering and Interpreting Liver Imaging.

PubMed

Sheybani, Arman; Gaba, Ron C; Lokken, R Peter; Berggruen, Senta M; Mar, Winnie A

2017-10-18

This paper reviews diagnostic imaging techniques used to characterize liver masses and the imaging characteristics of the most common liver masses. The role of recently adopted ultrasound and magnetic resonance imaging contrast agents will be emphasized. Contrast-enhanced ultrasound is an inexpensive exam which can confirm benignity of certain liver masses without ionizing radiation. Magnetic resonance imaging using hepatocyte-specific gadolinium-based contrast agents can help confirm or narrow the differential diagnosis of liver masses.

Dynamic imaging of protein-protein interactions by MP-FLIM

NASA Astrophysics Data System (ADS)

Ameer-Beg, Simon M.; Peter, Marion; Keppler, Melanie D.; Prag, Soren; Barber, Paul R.; Ng, Tony C.; Vojnovic, Borivoj

2005-03-01

The spatio-temporal localization of molecular interactions within cells in situ is of great importance in elucidating the key mechanisms in regulation of fundamental process within the cell. Measurements of such near-field localization of protein complexes may be achieved by the detection of fluorescence (or Forster) resonance energy transfer (FRET) between protein-conjugated fluorophores. We demonstrate the applicability of time-correlated single photon counting multiphoton microscopy to the spatio-temporal localization of protein-protein interactions in live and fixed cell populations. Intramolecular interactions between protein hetero-dimers are investigated using green fluorescent protein variants. We present an improved monomeric form of the red fluorescent protein, mRFP1, as the acceptor in biological fluorescence resonance energy transfer (FRET) experiments using the enhanced green fluorescent protein as donor. We find particular advantage in using this fluorophore pair for quantitative measurements of FRET. The technique was exploited to demonstrate a novel receptor-kinase interaction between the chemokine receptor (CXCR4) and protein kinase C (PKC) α in carcinoma cells for both live and fixed cell experiments.

Dramatic enhancement of supercontinuum generation in elliptically-polarized laser filaments

PubMed Central

Rostami, Shermineh; Chini, Michael; Lim, Khan; Palastro, John P.; Durand, Magali; Diels, Jean-Claude; Arissian, Ladan; Baudelet, Matthieu; Richardson, Martin

2016-01-01

Broadband laser sources based on supercontinuum generation in femtosecond laser filamentation have enabled applications from stand-off sensing and spectroscopy to the generation and self-compression of high-energy few-cycle pulses. Filamentation relies on the dynamic balance between self-focusing and plasma defocusing – mediated by the Kerr nonlinearity and multiphoton or tunnel ionization, respectively. The filament properties, including the supercontinuum generation, are therefore highly sensitive to the properties of both the laser source and the propagation medium. Here, we report the anomalous spectral broadening of the supercontinuum for filamentation in molecular gases, which is observed for specific elliptical polarization states of the input laser pulse. The resulting spectrum is accompanied by a modification of the supercontinuum polarization state and a lengthening of the filament plasma column. Our experimental results and accompanying simulations suggest that rotational dynamics of diatomic molecules play an essential role in filamentation-induced supercontinuum generation, which can be controlled with polarization ellipticity. PMID:26847427

Mass Spectroscopy of Neutral Metal Oxide Clusters Using a Desk-Top Soft X-Ray Laser

NASA Astrophysics Data System (ADS)

Dong, F.; Heinbuch, S.; Bernstein, E. R.; Rocca, J. J.

We report the use of a compact 46.9 nm capillary discharge soft x-ray laser in the study of metal-oxide nanoclusters using mass spectroscopy. Transition metal oxides are widely used as heterogeneous catalysts and catalytic supports in industrial processes. There are numerous applications for transition metal oxide catalysts, and although they are widely used, there is a lack of fundamental understanding of the complicated processes that occur on the metal oxide surface during catalysis. Conventional nanocluster spectroscopy techniques have used 193 nm radiation from an ArF excimer laser corresponding to a photon energy of 6.4 eV in order to photoionize a sample. Typical metal oxide nanocluster ionization energies fall into the range of 7-12 eV while some have even higher energies. Therefore a single 6.4 eV photon can not ionize the cluster making multiphoton processes the dominant ionization method. A major problem associated with mass spectroscopy can become evident during the multiphoton ionization of clusters. Specifically, the clusters may fragment during the ionization process and the identification of the neutral parent cluster can become difficult. In the present experiment neutral vanadium, niobium and tantalum oxide clusters are studied by single photon ionization with the 26.5 eV photons produced by a capillary discharge soft x-ray laser.1 During ionization, the metal oxide clusters are observed to be almost free of serious fragmentation. The most stable neutral cluster of vanadium, niobium, and tantalum oxide growth in a saturated oxygen condition are identified as MO2, M2O4/M2O5, M3O7, M4O10, M5O12, M6O15, M7O17, M8O20, and M9O22, which can be represented as a form (MO2)0,1(M2O5)y. M2O5 is identified as a basic unit to build-up the three kinds of metal oxide clusters. In the case of niobium and tantalum oxide clusters, the oxygen-deficient clusters with a structure of (MO2)2(M2O5)y are detected for groups that contain an even number of metal atoms. For vanadium oxide clusters, the oxygen-deficient clusters are detected for every family, indicating a stable structure of (VO2)x(V2O5)y. The stoichiometry of oxygen-rich clusters can be expressed as (MO2)0,1(M2O5)yO1-3 and their structures are consistent with chemically bonded species.

Disentangling Intracycle Interferences in Photoelectron Momentum Distributions Using Orthogonal Two-Color Laser Fields

NASA Astrophysics Data System (ADS)

Xie, Xinhua; Wang, Tian; Yu, ShaoGang; Lai, XuanYang; Roither, Stefan; Kartashov, Daniil; Baltuška, Andrius; Liu, XiaoJun; Staudte, André; Kitzler, Markus

2017-12-01

We use orthogonally polarized two-color (OTC) laser pulses to separate quantum paths in the multiphoton ionization of Ar atoms. Our OTC pulses consist of 400 and 800 nm light at a relative intensity ratio of 10 ∶1 . We find a hitherto unobserved interference in the photoelectron momentum distribution, which exhibits a strong dependence on the relative phase of the OTC pulse. Analysis of model calculations reveals that the interference is caused by quantum pathways from nonadjacent quarter cycles.

Carrier-envelope phase-dependent atomic coherence and quantum beats

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

Wu Ying; State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071; Yang Xiaoxue

2007-07-15

It is shown that the carrier-envelope phase (CEP) of few-cycle laser pulses has profound effects on the bound-state atomic coherence even in the weak-field regime where both tunneling and multiphoton ionization hardly take place. The atomic coherence thus produced is shown to be able to be mapped onto the CEP-dependent signal of quantum beats (and other quantum-interference phenomena) and hence might be used to extract information about and ultimately to measure the carrier-envelope phase.

Theoretical derivation of laser-dressed atomic states by using a fractal space

NASA Astrophysics Data System (ADS)

Duchateau, Guillaume

2018-05-01

The derivation of approximate wave functions for an electron submitted to both a Coulomb and a time-dependent laser electric fields, the so-called Coulomb-Volkov (CV) state, is addressed. Despite its derivation for continuum states does not exhibit any particular problem within the framework of the standard theory of quantum mechanics (QM), difficulties arise when considering an initially bound atomic state. Indeed the natural way of translating the unperturbed momentum by the laser vector potential is no longer possible since a bound state does not exhibit a plane wave form explicitly including a momentum. The use of a fractal space permits to naturally define a momentum for a bound wave function. Within this framework, it is shown how the derivation of laser-dressed bound states can be performed. Based on a generalized eikonal approach, a new expression for the laser-dressed states is also derived, fully symmetric relative to the continuum or bound nature of the initial unperturbed wave function. It includes an additional crossed term in the Volkov phase which was not obtained within the standard theory of quantum mechanics. The derivations within this fractal framework have highlighted other possible ways to derive approximate laser-dressed states in QM. After comparing the various obtained wave functions, an application to the prediction of the ionization probability of hydrogen targets by attosecond XUV pulses within the sudden approximation is provided. This approach allows to make predictions in various regimes depending on the laser intensity, going from the non-resonant multiphoton absorption to tunneling and barrier-suppression ionization.

A least squares approach to estimating the probability distribution of unobserved data in multiphoton microscopy

NASA Astrophysics Data System (ADS)

Salama, Paul

2008-02-01

Multi-photon microscopy has provided biologists with unprecedented opportunities for high resolution imaging deep into tissues. Unfortunately deep tissue multi-photon microscopy images are in general noisy since they are acquired at low photon counts. To aid in the analysis and segmentation of such images it is sometimes necessary to initially enhance the acquired images. One way to enhance an image is to find the maximum a posteriori (MAP) estimate of each pixel comprising an image, which is achieved by finding a constrained least squares estimate of the unknown distribution. In arriving at the distribution it is assumed that the noise is Poisson distributed, the true but unknown pixel values assume a probability mass function over a finite set of non-negative values, and since the observed data also assumes finite values because of low photon counts, the sum of the probabilities of the observed pixel values (obtained from the histogram of the acquired pixel values) is less than one. Experimental results demonstrate that it is possible to closely estimate the unknown probability mass function with these assumptions.

Quasistatic limit of the strong-field approximation describing atoms in intense laser fields: Circular polarization

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

Bauer, Jaroslaw H.

2011-03-15

In the recent work of Vanne and Saenz [Phys. Rev. A 75, 063403 (2007)] the quasistatic limit of the velocity gauge strong-field approximation describing the ionization rate of atomic or molecular systems exposed to linearly polarized laser fields was derived. It was shown that in the low-frequency limit the ionization rate is proportional to the laser frequency {omega} (for a constant intensity of the laser field). In the present work I show that for circularly polarized laser fields the ionization rate is proportional to {omega}{sup 4} for H(1s) and H(2s) atoms, to {omega}{sup 6} for H(2p{sub x}) and H(2p{sub y})more » atoms, and to {omega}{sup 8} for H(2p{sub z}) atoms. The analytical expressions for asymptotic ionization rates (which become nearly accurate in the limit {omega}{yields}0) contain no summations over multiphoton contributions. For very low laser frequencies (optical or infrared) these expressions usually remain with an order-of-magnitude agreement with the velocity gauge strong-field approximation.« less

High-order above-threshold dissociation of molecules

NASA Astrophysics Data System (ADS)

Lu, Peifen; Wang, Junping; Li, Hui; Lin, Kang; Gong, Xiaochun; Song, Qiying; Ji, Qinying; Zhang, Wenbin; Ma, Junyang; Li, Hanxiao; Zeng, Heping; He, Feng; Wu, Jian

2018-03-01

Electrons bound to atoms or molecules can simultaneously absorb multiple photons via the above-threshold ionization featured with discrete peaks in the photoelectron spectrum on account of the quantized nature of the light energy. Analogously, the above-threshold dissociation of molecules has been proposed to address the multiple-photon energy deposition in the nuclei of molecules. In this case, nuclear energy spectra consisting of photon-energy spaced peaks exceeding the binding energy of the molecular bond are predicted. Although the observation of such phenomena is difficult, this scenario is nevertheless logical and is based on the fundamental laws. Here, we report conclusive experimental observation of high-order above-threshold dissociation of H2 in strong laser fields where the tunneling-ionized electron transfers the absorbed multiphoton energy, which is above the ionization threshold to the nuclei via the field-driven inelastic rescattering. Our results provide an unambiguous evidence that the electron and nuclei of a molecule as a whole absorb multiple photons, and thus above-threshold ionization and above-threshold dissociation must appear simultaneously, which is the cornerstone of the nowadays strong-field molecular physics.

Ionization cross section, pressure shift and isotope shift measurements of osmium

NASA Astrophysics Data System (ADS)

Hirayama, Yoshikazu; Mukai, Momo; Watanabe, Yutaka; Oyaizu, Michihiro; Ahmed, Murad; Kakiguchi, Yutaka; Kimura, Sota; Miyatake, Hiroari; Schury, Peter; Wada, Michiharu; Jeong, Sun-Chan

2017-11-01

In-gas-cell laser resonance ionization spectroscopy of neutral osmium atoms was performed with the use of a two-color two-step laser resonance ionization technique. Saturation curves for the ionization scheme were measured, and the ionization cross section was experimentally determined by solving the rate equations for the ground, intermediate and ionization continuum populations. The pressure shift and pressure broadening in the resonance spectra of the excitation transition were measured. The electronic factor {F}247 for the transition {λ }1=247.7583 nm to the intermediate state was deduced from the measured isotope shifts of stable {}{188,189,{190,192}}Os isotopes. The efficient ionization scheme, pressure shift, nuclear isotope shift and {F}247 are expected to be useful for applications of laser ion sources to unstable nuclei and for nuclear spectroscopy based on laser ionization techniques.

Enhanced photoelectric detection of NV magnetic resonances in diamond under dual-beam excitation

NASA Astrophysics Data System (ADS)

Bourgeois, E.; Londero, E.; Buczak, K.; Hruby, J.; Gulka, M.; Balasubramaniam, Y.; Wachter, G.; Stursa, J.; Dobes, K.; Aumayr, F.; Trupke, M.; Gali, A.; Nesladek, M.

2017-01-01

The core issue for the implementation of NV center qubit technology is a sensitive readout of the NV spin state. We present here a detailed theoretical and experimental study of NV center photoionization processes, used as a basis for the design of a dual-beam photoelectric method for the detection of NV magnetic resonances (PDMR). This scheme, based on NV one-photon ionization, is significantly more efficient than the previously reported single-beam excitation scheme. We demonstrate this technique on small ensembles of ˜10 shallow NVs implanted in electronic grade diamond (a relevant material for quantum technology), on which we achieve a cw magnetic resonance contrast of 9%—three times enhanced compared to previous work. The dual-beam PDMR scheme allows independent control of the photoionization rate and spin magnetic resonance contrast. Under a similar excitation, we obtain a significantly higher photocurrent, and thus an improved signal-to-noise ratio, compared to single-beam PDMR. Finally, this scheme is predicted to enhance magnetic resonance contrast in the case of samples with a high proportion of substitutional nitrogen defects, and could therefore enable the photoelectric readout of single NV spins.

Observation of fullerenes (C60-C70) associated with LDEF crater number 31

NASA Technical Reports Server (NTRS)

Radicatidibrozolo, Filippo; Fleming, R. H.; Bunch, T. E.

1992-01-01

The presence of fullerenes in and around the LDEF crater number 31 is reported. This crater has a high C level associated with it, and is interpreted as having been produced by the impact of a C-rich micrometeoroid. Fullerenes are large 3-D C structures, among which the species C sub 60 (MW 720) and C sub 70 (MW 840) are preeminent. Fullerenes have several UV absorption bands, hence fullerenes should be detectable using UV laser ionization time-of-flight mass spectrometry. We use a LIMA-2A instrument with pulsed UV laser (266 nm) to search for high mass C species associated with LDEF crater number 31. The mass range was 0 to 1200 amu. Low ablating laser power levels were used (less than or = 5 x 10 exp 7 W/sq. cm); 200 mass spectra were acquired and summed. We observed high mass signals near m/z 720, exhibiting 24 amu separation, which is characteristic of fullerenes. Alkali ion signals were also observed. Little or no C clusters of intermediate mass were observed. We interpret the signals around m/z 720 as fullerenes, mainly C sub 60+ with lower levels of C sub 70+. We propose that the mechanism that produces these signals is resonant multiphoton ionization (REMPI). This selective mechanism explains why low mass C cluster ions are not observed along with the fullerenes, since they have much higher ionization potentials. This finding is unexpected, since up to now the search for fullerenes in extraterrestrial materials has not been successful. We conclude that the fullerenes became associated with crater number 31 in space. Two alternative (and exciting) scenarios are being considered at this time: either the fullerenes were carried by the C-rich projectile that formed crater number 31, or the fullerenes formed upon impact with the LDEF. We show the results of experiments at the ARC Vertical Gun Facility, which may establish some constraints on the origin of the fullerenes.

Circular dichroism in photoelectron images from aligned nitric oxide molecules

DOE PAGES

Sen, Ananya; Pratt, S. T.; Reid, K. L.

2017-05-03

We have used velocity map photoelectron imaging to study circular dichroism of the photoelectron angular distributions (PADs) of nitric oxide following two-color resonanceenhanced two-photon ionization via selected rotational levels of the A 2Σ +, v' = 0 state. By using a circularly polarized pump beam and a counter-propagating, circularly polarized probe beam, cylindrical symmetry is preserved in the ionization process, and the images can be reconstructed using standard algorithms. The VMI set up enables individual ion rotational states to be resolved with excellent collection efficiency, rendering the measurements considerably simpler to perform than previous measurements conducted with a conventional photoelectronmore » spectrometer. The results demonstrate that circular dichroism is observed even when cylindrical symmetry is maintained, and serve as a reminder that dichroism is a general feature of the multiphoton ionization of atoms and molecules. Furthermore, the observed PADs are in good agreement with calculations based on parameters extracted from previous experimental results obtained by using a time-offlight electron spectrometer.« less

Circular dichroism in photoelectron images from aligned nitric oxide molecules

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

Sen, Ananya; Pratt, S. T.; Reid, K. L.

We have used velocity map photoelectron imaging to study circular dichroism of the photoelectron angular distributions (PADs) of nitric oxide following two-color resonanceenhanced two-photon ionization via selected rotational levels of the A 2Σ +, v' = 0 state. By using a circularly polarized pump beam and a counter-propagating, circularly polarized probe beam, cylindrical symmetry is preserved in the ionization process, and the images can be reconstructed using standard algorithms. The VMI set up enables individual ion rotational states to be resolved with excellent collection efficiency, rendering the measurements considerably simpler to perform than previous measurements conducted with a conventional photoelectronmore » spectrometer. The results demonstrate that circular dichroism is observed even when cylindrical symmetry is maintained, and serve as a reminder that dichroism is a general feature of the multiphoton ionization of atoms and molecules. Furthermore, the observed PADs are in good agreement with calculations based on parameters extracted from previous experimental results obtained by using a time-offlight electron spectrometer.« less

Five-Photon Absorption and Selective Enhancement of Multiphoton Absorption Processes

PubMed Central

2015-01-01

We study one-, two-, three-, four-, and five-photon absorption of three centrosymmetric molecules using density functional theory. These calculations are the first ab initio calculations of five-photon absorption. Even- and odd-order absorption processes show different trends in the absorption cross sections. The behavior of all even- and odd-photon absorption properties shows a semiquantitative similarity, which can be explained using few-state models. This analysis shows that odd-photon absorption processes are largely determined by the one-photon absorption strength, whereas all even-photon absorption strengths are largely dominated by the two-photon absorption strength, in both cases modulated by powers of the polarizability of the final excited state. We demonstrate how to selectively enhance a specific multiphoton absorption process. PMID:26120588

Five-Photon Absorption and Selective Enhancement of Multiphoton Absorption Processes.

PubMed

Friese, Daniel H; Bast, Radovan; Ruud, Kenneth

2015-05-20

We study one-, two-, three-, four-, and five-photon absorption of three centrosymmetric molecules using density functional theory. These calculations are the first ab initio calculations of five-photon absorption. Even- and odd-order absorption processes show different trends in the absorption cross sections. The behavior of all even- and odd-photon absorption properties shows a semiquantitative similarity, which can be explained using few-state models. This analysis shows that odd-photon absorption processes are largely determined by the one-photon absorption strength, whereas all even-photon absorption strengths are largely dominated by the two-photon absorption strength, in both cases modulated by powers of the polarizability of the final excited state. We demonstrate how to selectively enhance a specific multiphoton absorption process.

Cornea surgery with nanojoule femtosecond laser pulses

NASA Astrophysics Data System (ADS)

Koenig, Karsten; Wang, Bagui; Riemann, Iris; Kobow, Jens

2005-04-01

We report on a novel optical method for (i) flap-generation in LASIK procedures as well as (ii) for flap-free intrastromal refractive surgery based on nanojoule femtosecond laser pulses. The near infrared 200 fs pulses for multiphoton ablation have been provided by ultracompact turn-key MHz laser resonators. LASIK flaps and intracorneal cavities have been realized with high precision within living New Zealand rabbits using the system FemtoCutO (JenLab GmbH, Jena, Germany) at 800 nm laser wavelength. Using low-energy sub-2 nJ laser pulses, collateral damage due to photodisruptive and self-focusing effects was avoided. The laser ablation system consists of fast galvoscanners, focusing optics of high numerical aperture as well as a sensitive imaging system and provides also the possibility of 3D multiphoton imaging of fluorescent cellular organelles and SHG signals from collagen. Multiphoton tomography of the cornea was used to determine the exact intratissue beam position and to visualize intraocular post-laser effects. The wound healing process has been investigated up to 90 days after instrastromal laser ablation by histological analysis. Regeneration of damaged collagen structures and the migration of inflammation cells have been detected.

Resonance-modulated wavelength scaling of high-order-harmonic generation from H2+

NASA Astrophysics Data System (ADS)

Wang, Baoning; He, Lixin; Wang, Feng; Yuan, Hua; Zhu, Xiaosong; Lan, Pengfei; Lu, Peixiang

2018-01-01

Wavelength scaling of high-order harmonic generation (HHG) in a non-Born-Oppenheimer treatment of H2+ is investigated by numerical simulations of the time-dependent Schrödinger equation. The results show that the decrease in the wavelength-dependent HHG yield is reduced compared to that in the fixed-nucleus approximation. This slower wavelength scaling is related to the charge-resonance-enhanced ionization effect, which considerably increases the ionization rate at longer driving laser wavelengths due to the relatively larger nuclear separation. In addition, we find an oscillation structure in the wavelength scaling of HHG from H2+. Upon decreasing the laser intensity or increasing the nuclear mass, the oscillation structure will shift towards a longer wavelength of the laser pulse. These results permit the generation of an efficient harmonic spectrum in the midinfrared regime by manipulating the nuclear dynamics of molecules.

Photon-number-resolving SSPDs with system detection efficiency over 50% at telecom range

NASA Astrophysics Data System (ADS)

Zolotov, P.; Divochiy, A.; Vakhtomin, Yu.; Moshkova, M.; Morozov, P.; Seleznev, V.; Smirnov, K.

2018-02-01

We used technology of making high-efficiency superconducting single-photon detectors as a basis for improvement of photon-number-resolving devices. By adding optical cavity and using an improved NbN superconducting film, we enhanced previously reported system detection efficiency at telecom range for such detectors. Our results show that implementation of optical cavity helps to develop four-section device with quantum efficiency over 50% at 1.55 µm. Performed experimental studies of detecting multi-photon optical pulses showed irregularities over defining multi-photon through single-photon quantum efficiency.

Bright nanoscale source of deterministic entangled photon pairs violating Bell's inequality.

PubMed

Jöns, Klaus D; Schweickert, Lucas; Versteegh, Marijn A M; Dalacu, Dan; Poole, Philip J; Gulinatti, Angelo; Giudice, Andrea; Zwiller, Val; Reimer, Michael E

2017-05-10

Global, secure quantum channels will require efficient distribution of entangled photons. Long distance, low-loss interconnects can only be realized using photons as quantum information carriers. However, a quantum light source combining both high qubit fidelity and on-demand bright emission has proven elusive. Here, we show a bright photonic nanostructure generating polarization-entangled photon pairs that strongly violates Bell's inequality. A highly symmetric InAsP quantum dot generating entangled photons is encapsulated in a tapered nanowire waveguide to ensure directional emission and efficient light extraction. We collect ~200 kHz entangled photon pairs at the first lens under 80 MHz pulsed excitation, which is a 20 times enhancement as compared to a bare quantum dot without a photonic nanostructure. The performed Bell test using the Clauser-Horne-Shimony-Holt inequality reveals a clear violation (S CHSH  > 2) by up to 9.3 standard deviations. By using a novel quasi-resonant excitation scheme at the wurtzite InP nanowire resonance to reduce multi-photon emission, the entanglement fidelity (F = 0.817 ± 0.002) is further enhanced without temporal post-selection, allowing for the violation of Bell's inequality in the rectilinear-circular basis by 25 standard deviations. Our results on nanowire-based quantum light sources highlight their potential application in secure data communication utilizing measurement-device-independent quantum key distribution and quantum repeater protocols.

Photoionization and electron-impact ionization of Ar5+

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

Wang, J.C.; Lu, M.; Esteves, D.

2007-02-27

Absolute cross sections for photoionization andelectron-impact Photionization of Ar5+ have been measuredusing twodifferent interacting-beams setups. The spectra consist of measurementsof the yield of products dueto single ionization as a function ofelectron or photon energy. In addition, absolute photoionization andelectron-impact ionization cross sections were measured to normalize themeasured Ar6+ product-ion yield spectra. In the energy range from 90 to111 eV, both electron-impact ionization and photoionization of Ar5+aredominated by indirect 3s subshell excitation-autoionization. In theenergy range from 270 to 285 eV, resonances due to 2p-3dexcitation-autoionization are prominent in the photoionization spectrum.In the range from 225 to 335 eV, an enhancement due tomore » 2p-nl (n>2>excitations are evident in the electron-impactionization cross section.The electron and photon impact data show some features due to excitationof the same intermediate autoionizing states.« less

Laser-induced radiation microbeam technology and simultaneous real-time fluorescence imaging in live cells.

PubMed

Botchway, Stanley W; Reynolds, Pamela; Parker, Anthony W; O'Neill, Peter

2012-01-01

The use of nano- and microbeam techniques to induce and identify subcellular localized energy deposition within a region of a living cell provides a means to investigate the effects of low radiation doses. Particularly within the nucleus where the propagation and processing of deoxyribonucleic acid (DNA) damage (and repair) in both targeted and nontargeted cells, the latter being able to study cell-cell (bystander) effects. We have pioneered a near infrared (NIR) femtosecond laser microbeam to mimic ionizing radiation through multiphoton absorption within a 3D femtoliter volume of a highly focused Gaussian laser beam. The novel optical microbeam mimics both complex ionizing and UV-radiation-type cell damage including double strand breaks (DSBs). Using the microbeam technology, we have been able to investigate the formation of DNA DSB and subsequent recruitment of repair proteins to the submicrometer size site of damage introduced in viable cells. The use of a phosphorylated H2AX (γ-H2AX a marker for DSBs, visualized by immunofluorescent staining) and real-time imaging of fluorescently labeling proteins, the dynamics of recruitment of repair proteins in viable mammalian cells can be observed. Here we show the recruitment of ATM, p53 binding protein 1 (53BP1), and RAD51, an integral protein of the homologous recombination process in the DNA repair pathway and Ku-80-GFP involved in the nonhomologous end joining (NHEJ) pathway as exemplar repair process to show differences in the repair kinetics of DNA DSBs. The laser NIR multiphoton microbeam technology shows persistent DSBs at later times post laser irradiation which are indicative of DSBs arising at replication presumably from UV photoproducts or clustered damage containing single strand breaks (SSBs) that are also observed. Effects of the cell cycle may also be investigated in real time. Postirradiation and fixed cells studies show that in G1 cells a fraction of multiphoton laser-induced DSBs is persistent for >6h in addition to those induced at replication demonstrating the broad range of timescales taken to repair DNA damage. Copyright © 2012 Elsevier Inc. All rights reserved.

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

Heslar, John; Chu, Shih-I.

Recently, the study of near- and below- threshold regime harmonics as a potential source of intense coherent vacuum-ultraviolet radiation has received considerable attention. However, the dynamical origin of these lower harmonics, particularly for the molecular systems, is less understood and largely unexplored. Here we perform the first fully ab initio and high precision 3D quantum study of the below- and near-threshold harmonic generation of H 2 + molecules in an intense 800-nm near-infrared (NIR) laser field. Furthermore, combining with a synchrosqueezing transform of the quantum time-frequency spectrum and an extended semiclassical analysis, we explore in-depth the roles of various quantummore » trajectories, including short- and long trajectories, multiphoton trajectories, resonance-enhanced trajectories, and multiple rescattering trajectories of the below- and near- threshold harmonic generation processes. Our results shed new light on the dynamical origin of the below- and near-threshold harmonic generation and various quantum trajectories for diatomic molecules for the first time.« less

OSA (Optical Society of America) Proceedings on Short Wavelength Coherent Radiation: Generation and Applications Held in North Falmouth, Massachusetts on 26-29 September 1988. Volume 2

DTIC Science & Technology

1988-09-01

obtained using CVI 6d-2p line 142 Axial as a reference line[5]. The maximum en- hancement factor of 4.2 and corresponding cv1 gain length product of...C. Solem, and C. K. Rhodes ..... .............. 220 Multiphoton Ionization for the Production of X-Ray Laser Plasmas by P. B. Corkum and N. H...Diffraction Using Synchrotron Radiation by Rudolf Ruffer ......... ............................... 400 The Production of Long Coherence-Length Hard X

Free Radical-Surface Interactions Using Multiphoton Ionization of Free Radicals

DTIC Science & Technology

1989-01-01

Atoms, Rgf4PI 9 t Free Radl!cals)aj" i Atoms, Cross Section -’r RE)* I of Free Radicals arid Atonn. 𔄃 43S’RACT (Conti n reverse if necessary Ind identi...these surfaces. The basic philosophy of our CF 3I -+- nhv-CF, - t - I . program consists of generating a particular neutral species at A low pressures...constant for the escape of radicals out of the " reactor is shown in Eq. (6): .= k =, 4 .4,., I /V, (6) L !J 7 where t ,,, is the thermal molecular

Single-shot measurements of laser-induced avalanche breakdown demonstrating spatial and temporal control by an external source

NASA Astrophysics Data System (ADS)

Woodbury, Daniel; Wahlstrand, Jared; Goers, Andy; Feder, Linus; Miao, Bo; Hine, George; Salehi, Fatholah; Milchberg, Howard

2016-10-01

We report on the use of single-shot supercontinuum spectral interferometry (SSSI) to make temporally and spatially resolved measurements of laser-induced avalanche breakdown in ambient air by a 200 ps pulse. By seeding the breakdown using an external 100 fs pulse, we demonstrate control over the timing and spatial characteristics of the avalanche. In addition, we calculate the collisional ionization rates at various laser intensities and demonstrate seeding of the avalanche breakdown both by multiphoton ionization and by photodetaching ions produced from a radioactive source. These observations provide proof-of-concept support for recent proposals to remotely measure radioactivity using laser-induced avalanche breakdown. This work supported by a DTRA, C-WMD Basic Research Program, and by the DOE NNSA Stewardship Science Graduate Fellowship, provided under Grant Number DE-NA0002135.

High-order above-threshold dissociation of molecules.

PubMed

Lu, Peifen; Wang, Junping; Li, Hui; Lin, Kang; Gong, Xiaochun; Song, Qiying; Ji, Qinying; Zhang, Wenbin; Ma, Junyang; Li, Hanxiao; Zeng, Heping; He, Feng; Wu, Jian

2018-02-27

Electrons bound to atoms or molecules can simultaneously absorb multiple photons via the above-threshold ionization featured with discrete peaks in the photoelectron spectrum on account of the quantized nature of the light energy. Analogously, the above-threshold dissociation of molecules has been proposed to address the multiple-photon energy deposition in the nuclei of molecules. In this case, nuclear energy spectra consisting of photon-energy spaced peaks exceeding the binding energy of the molecular bond are predicted. Although the observation of such phenomena is difficult, this scenario is nevertheless logical and is based on the fundamental laws. Here, we report conclusive experimental observation of high-order above-threshold dissociation of H 2 in strong laser fields where the tunneling-ionized electron transfers the absorbed multiphoton energy, which is above the ionization threshold to the nuclei via the field-driven inelastic rescattering. Our results provide an unambiguous evidence that the electron and nuclei of a molecule as a whole absorb multiple photons, and thus above-threshold ionization and above-threshold dissociation must appear simultaneously, which is the cornerstone of the nowadays strong-field molecular physics. Copyright © 2018 the Author(s). Published by PNAS.

Rapid Profiling of Bovine and Human Milk Gangliosides by Matrix-Assisted Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

PubMed Central

Lee, Hyeyoung; An, Hyun Joo; Lerno, Larry A.; German, J. Bruce; Lebrilla, Carlito B.

2010-01-01

Gangliosides are anionic glycosphingolipids widely distributed in vertebrate tissues and fluids. Their structural and quantitative expression patterns depend on phylogeny and are distinct down to the species level. In milk, gangliosides are exclusively associated with the milk fat globule membrane. They may participate in diverse biological processes but more specifically to host-pathogen interactions. However, due to the molecular complexities, the analysis needs extensive sample preparation, chromatographic separation, and even chemical reaction, which makes the process very complex and time-consuming. Here, we describe a rapid profiling method for bovine and human milk gangliosides employing matrix-assisted desorption/ionization (MALDI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS). Prior to the analyses of biological samples, milk ganglioside standards GM3 and GD3 fractions were first analyzed in order to validate this method. High mass accuracy and high resolution obtained from MALDI FTICR MS allow for the confident assignment of chain length and degree of unsaturation of the ceramide. For the structural elucidation, tandem mass spectrometry (MS/MS), specifically as collision-induced dissociation (CID) and infrared multiphoton dissociation (IRMPD) were employed. Complex ganglioside mixtures from bovine and human milk were further analyzed with this method. The samples were prepared by two consecutive chloroform/methanol extraction and solid phase extraction. We observed a number of differences between bovine milk and human milk. The common gangliosides in bovine and human milk are NeuAc-NeuAc-Hex-Hex-Cer (GD3) and NeuAc-Hex-Hex-Cer (GM3); whereas, the ion intensities of ganglioside species are different between two milk samples. Kendrick mass defect plot yields grouping of ganglioside peaks according to their structural similarities. Gangliosides were further probed by tandem MS to confirm the compositional and structural assignments. We found that only in human milk gangliosides was the ceramide carbon always even numbered, which is consistent with the notion that differences in the oligosaccharide and the ceramide moieties confer to their physiological distinctions. PMID:21860602

How the laser-induced ionization of transparent solids can be suppressed

NASA Astrophysics Data System (ADS)

Gruzdev, Vitaly

2013-12-01

A capability to suppress laser-induced ionization of dielectric crystals in controlled and predictable way can potentially result in substantial improvement of laser damage threshold of optical materials. The traditional models that employ the Keldysh formula do not predict any suppression of the ionization because of the oversimplified description of electronic energy bands underlying the Keldysh formula. To fix this gap, we performed numerical simulations of time evolution of conduction-band electron density for a realistic cosine model of electronic bands characteristic of wide-band-gap cubic crystals. The simulations include contributions from the photo-ionization (evaluated by the Keldysh formula and by the formula for the cosine band of volume-centered cubic crystals) and from the avalanche ionization (evaluated by the Drude model). Maximum conduction-band electron density is evaluated from a single rate equation as a function of peak intensity of femtosecond laser pulses for alkali halide crystals. Results obtained for high-intensity femtosecond laser pulses demonstrate that the ionization can be suppressed by proper choice of laser parameters. In case of the Keldysh formula, the peak electron density exhibits saturation followed by gradual increase. For the cosine band, the electron density increases with irradiance within the low-intensity multiphoton regime and switches to decrease with intensity approaching threshold of the strong singularity of the ionization rate characteristic of the cosine band. Those trends are explained with specific modifications of band structure by electric field of laser pulses.

Classical subharmonic resonances in microwave ionization of lithium Rydberg atoms

NASA Astrophysics Data System (ADS)

Noel, Michael W.; Griffith, W. M.; Gallagher, T. F.

2000-12-01

We have studied the ionization of lithium Rydberg atoms by pulsed microwave fields in the regime in which the microwave frequency is equal to or a subharmonic of the classical Kepler frequency of the two-body Coulomb problem. We have observed a series of resonances where the atom is relatively stable against ionization. The resonances are similar to those seen previously in hydrogen, but with significant quantitative differences. We also present measurements of the distribution of states that remain bound after the microwave interaction for initial states near one of the classical subharmonic resonances.

High resolution resonance ionization imaging detector and method

DOEpatents

Winefordner, James D.; Matveev, Oleg I.; Smith, Benjamin W.

1999-01-01

A resonance ionization imaging device (RIID) and method for imaging objects using the RIID are provided, the RIID system including a RIID cell containing an ionizable vapor including monoisotopic atoms or molecules, the cell being positioned to intercept scattered radiation of a resonance wavelength .lambda..sub.1 from the object which is to be detected or imaged, a laser source disposed to illuminate the RIID cell with laser radiation having a wavelength .lambda..sub.2 or wavelengths .lambda..sub.2, .lambda..sub.3 selected to ionize atoms in the cell that are in an excited state by virtue of having absorbed the scattered resonance laser radiation, and a luminescent screen at the back surface of the RIID cell which presents an image of the number and position of charged particles present in the RIID cell as a result of the ionization of the excited state atoms. The method of the invention further includes the step of initially illuminating the object to be detected or imaged with a laser having a wavelength selected such that the object will scatter laser radiation having the resonance wavelength .lambda..sub.1.

Vibrational spectra and structures of neutral Si(m)C(n) clusters (m + n = 6): sequential doping of silicon clusters with carbon atoms.

PubMed

Savoca, Marco; Lagutschenkov, Anita; Langer, Judith; Harding, Dan J; Fielicke, André; Dopfer, Otto

2013-02-14

Vibrational spectra of mixed silicon carbide clusters Si(m)C(n) with m + n = 6 in the gas phase are obtained by resonant infrared-vacuum-ultraviolet two-color ionization (IR-UV2CI for n ≤ 2) and density functional theory (DFT) calculations. Si(m)C(n) clusters are produced in a laser vaporization source, in which the silicon plasma reacts with methane. Subsequently, they are irradiated with tunable IR light from an IR free electron laser before they are ionized with UV photons from an F(2) laser. Resonant absorption of one or more IR photons leads to an enhanced ionization efficiency for Si(m)C(n) and provides the size-specific IR spectra. IR spectra measured for Si(6), Si(5)C, and Si(4)C(2) are assigned to their most stable isomers by comparison with calculated linear absorption spectra. The preferred Si(m)C(n) structures with m + n = 6 illustrate the systematic transition from chain-like geometries for bare C(6) to three-dimensional structures for bare Si(6). In contrast to bulk SiC, carbon atom segregation is observed already for the smallest n (n = 2).

Multiresonant Composite Optical Nanoantennas by Out-of-plane Plasmonic Engineering.

PubMed

Song, Junyeob; Zhou, Wei

2018-06-27

Optical nanoantennas can concentrate light and enhance light-matter interactions in subwavelength domain, which is useful for photodetection, light emission, optical biosensing, and spectroscopy. However, conventional optical nanoantennas operating at a single wavelength band are not suitable for multiband applications. Here, we propose and exploit an out-of-plane plasmonic engineering strategy to design and create composite optical nanoantennas that can support multiple nanolocalized modes at different resonant wavelengths. These multiresonant composite nanoantennas are composed of vertically stacked building blocks of metal-insulator-metal loop nanoantennas. Studies of multiresonant composite nanoantennas demonstrate that the number of supported modes depends on the number of vertically stacked building blocks and the resonant wavelengths of individual modes are tunable by controlling the out-of-plane geometries of their building blocks. In addition, numerical studies show that the resonant wavelengths of individual modes in composite nanoantennas can deviate from the optical response of building blocks due to hybridization of magnetic modes in neighboring building blocks. Using Au nanohole arrays as deposition masks to fabricate arrays of multilayered composite nanoantennas, we experimentally demonstrate their multiresonant optical properties in good agreement with theory predictions. These studies show that out-of-plane engineered multiresonant composite nanoantennas can provide new opportunities for fundamental nanophotonics research and practical applications involving optical multiband operations, such as multiphoton process, broadband solar energy conversion, and wavelength-multiplexed optical system.

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.

Resonant recombination and autoionization in electron-ion collisions

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

Mueller, A.

1990-06-01

The occurence of resonances in elastic and inelastic electron-ion collisions is discussed. Resonant processes involve excitation of the ion with simultaneous capture of the initially free electron. The decay mechanism subsequent to the formation of the intermediate multiply excited state determines whether a resonance is found in recombination, excitation, elastic scattering, in single or even in multiple ionization. This review concentrates on resonances in the ionization channel. Correlated two-electron transitions are considered.

Physics of the Brain. Prevention of the Epileptic Seizures by the Multi-photon Pulsed-operated Fiber Lasers in the Ultraviolet Range of Frequencies.

NASA Astrophysics Data System (ADS)

Stefan, V. Alexander; IAPS Team

The novel study of the epileptogenesis mechanisms is proposed. It is based on the pulsed-operated (amplitude modulation) multi-photon (frequency modulation) fiber-laser interaction with the brain epilepsy-topion (the epilepsy onset area), so as to prevent the excessive electrical discharge (epileptic seizure) in the brain. The repetition frequency, Ω, matches the low frequency (epileptic) phonon waves in the brain. The laser repetition frequency (5-100 pulses per second) enables the resonance-scanning of the wide range of the phonon (possible epileptic-to-be) activity in the brain. The tunable fiber laser frequencies, Δω (multi photon operation), are in the ultraviolet frequency range, thus enabling monitoring of the electrical charge imbalance (within the 10s of milliseconds), and the DNA-corruption in the epilepsy-topion, as the possible cause of the disease. Supported by Nikola Tesla Labs., Stefan University.

On second harmonic generation and multiphoton-absorption induced luminescence from laser-reshaped silver nanoparticles embedded in glass.

PubMed

Zolotovskaya, S A; Tyrk, M A; Stalmashonak, A; Gillespie, W A; Abdolvand, A

2016-10-28

Spherical silver nanoparticles (NPs) of 30 nm diameter embedded in soda-lime glass were uniformly reshaped (elongated) after irradiation by a linearly polarised 250 fs pulsed laser operating within the NPs' surface plasmon resonance band. We observed second harmonic generation (SHG) and multiphoton-absorption-induced luminescence (MAIL) in the embedded laser-reshaped NPs upon picosecond (10 ps) pulsed laser excitation at 1064 nm. A complementary study of SHG and MAIL was conducted in soda-lime glass containing embedded, mechanically-reshaped silver NPs of a similar elongation ratio (aspect ratio) to the laser-reshaped NPs. This supports the notion that the observed difference in SHG and MAIL in the studied nanocomposite systems is due to the shape modification mechanism. The discrete dipole approximation method was used to assess the absorption and scattering cross-sections of the reshaped NPs with different elongation ratios.

Controlled energy deposition and void-like modification inside transparent solids by two-color tightly focused femtosecond laser pulses

NASA Astrophysics Data System (ADS)

Potemkin, Fedor; Mareev, Evgeniy; Bezsudnova, Yulia; Platonenko, Victor; Bravy, Boris; Gordienko, Vyacheslav

2017-04-01

We report a bulk void-like micromodification of fused silica using two-color μJ-energy level tightly focused (NA = 0.5) co-propagating seeding (visible, 0.62 μm) and heating (near-IR, 1.24 μm) femtosecond laser pulses with online third harmonic diagnostics of created microplasmas as well as subsequent laser-induced void-like defects. It has been shown experimentally and theoretically that production of seeding electrons through multiphoton ionization by visible laser pulses paves the way for controllability of the energy deposition and laser-induced micromodification via carrier heating by delayed infrared laser pulses inside the material. Experimental results demonstrate wide possibilities to increase the density of energy deposited up to 6 kJ cm-3 inside the dielectric by tight focusing of two color fs-laser pulses and elliptical polarization for infrared heating fs-laser pulses. The developed theoretical approach predicts the enhancement of deposited energy density up to 9 kJ cm-3 using longer (mid-IR) wavelengths for heating laser pulses.

Experiments and PIC simulations on liquid crystal plasma mirrors for pulse contrast enhancement

NASA Astrophysics Data System (ADS)

Cochran, G. E.; Poole, P. L.; Krygier, A.; Foster, P. S.; Scott, G. G.; Wilson, L. A.; Bailey, J.; Bourgeois, N.; Hernandez-Gomez, C.; Heery, R.; Purcell, J.; Neely, D.; Rajeev, P. P.; Freeman, R. R.; Schumacher, D. W.

2016-10-01

High pulse contrast is crucial for performing many experiments on high intensity lasers in order to minimize modification of the target surface by pre-pulse. This is often achieved through the use of solid dielectric plasma mirrors which can limit laser shot rates. Liquid crystal films, originally developed as variable thickness ion acceleration targets, have been demonstrated as effective plasma mirrors for pulse cleaning, reaching peak reflectivities over 70%. These films were used as plasma mirrors in an ion acceleration experiment on the Scarlet laser and the resultant increase in peak proton energy and change in acceleration direction will be discussed. Also presented here are novel 2D3V, LSP particle-in-cell simulations of dielectric plasma mirror operation. By including multiphoton ionization and dimensionality corrections, an excellent match to experiment is obtained over 4 decades in intensity. Analysis of pulse shortening and plasma critical surface behavior in these simulations will be discussed. Formation of thin films at 1.5 Hz will also be presented. Performed with support from the DARPA PULSE program through AMRDEC, from NNSA, and from OSC.

Autoionizing resonances in electron-impact ionization of O5+ ions

NASA Astrophysics Data System (ADS)

Müller, A.; Teng, H.; Hofmann, G.; Phaneuf, R. A.; Salzborn, E.

2000-12-01

We report on a detailed experimental and theoretical study of electron-impact ionization of O5+ ions. A high-resolution scan measurement of the K-shell excitation threshold region has been performed with statistical uncertainties as low as 0.03%. At this level of precision a wealth of features in the cross section arising from indirect ionization processes becomes visible, and even interference of direct ionization with resonant-excitation/auto-double-ionization (READI) is clearly observed. The experimental results are compared with R-matrix calculations that include both direct and indirect processes in a unified way. Radiative damping of autoionizing Li-like states is found to be about 10-15 %. The calculations almost perfectly reproduce most of the experimental resonance features found in the present measurement including READI. They also agree with the direct-ionization converged close-coupling results of I. Bray [J. Phys. B 28, L247 (1995)] and the absolute total ionization cross section measurement of K. Rinn et al. [Phys. Rev. A 36, 595 (1987)].

7.87 eV Laser Desorption Postionization Mass Spectrometry of Adsorbed and Covalently Bound Bisphenol A Diglycidyl Methacrylate

PubMed Central

Zhou, Manshui; Wu, Chunping; Akhmetov, Artem; Edirisinghe, Praneeth D.; Drummond, James L.; Hanley, Luke

2007-01-01

Bisphenol A diglycidyl methacrylate (Bis-GMA) was adsorbed onto or covalently bound to a porous silicon oxide surface. Laser desorption 10.5 eV postionization mass spectrometry (LDPI-MS) was previously demonstrated for surface analysis of adsorbed and surface bound Bis-GMA, but signal to noise levels were low and ion fragmentation was extensive. 7.87 eV postionization using the fluorine laser was demonstrated here for Bis-GMA. However, signal levels remained low for LDPI-MS of Bis-GMA as its ionization potential was only ∼7.8 eV, near threshold for single photon ionization by the 7.87 eV fluorine laser. It is known that aromatic tagging of molecular analytes can lower the overall IP of the tagged molecular complex, allowing 7.87 eV single photon ionization. Therefore, Bis-GMA was also derivatized with several tags whose IPs were either below or above 7.87 eV: the tag with an IP below 7.87 eV enhanced single photon ionization while the tags with higher IPs did not. However, signal intensities were enhanced by resonant laser desorption for two of the derivatized Bis-GMAs. Intact ions of Bis-GMA and its derivatives were generally observed by 7.87 eV LDPI-MS, consistent with the formation of ions with relatively little internal energy upon threshold single photon ionization. PMID:17449273

Nonlinear structured-illumination enhanced temporal focusing multiphoton excitation microscopy with a digital micromirror device.

PubMed

Cheng, Li-Chung; Lien, Chi-Hsiang; Da Sie, Yong; Hu, Yvonne Yuling; Lin, Chun-Yu; Chien, Fan-Ching; Xu, Chris; Dong, Chen Yuan; Chen, Shean-Jen

2014-08-01

In this study, the light diffraction of temporal focusing multiphoton excitation microscopy (TFMPEM) and the excitation patterning of nonlinear structured-illumination microscopy (NSIM) can be simultaneously and accurately implemented via a single high-resolution digital micromirror device. The lateral and axial spatial resolutions of the TFMPEM are remarkably improved through the second-order NSIM and projected structured light, respectively. The experimental results demonstrate that the lateral and axial resolutions are enhanced from 397 nm to 168 nm (2.4-fold) and from 2.33 μm to 1.22 μm (1.9-fold), respectively, in full width at the half maximum. Furthermore, a three-dimensionally rendered image of a cytoskeleton cell featuring ~25 nm microtubules is improved, with other microtubules at a distance near the lateral resolution of 168 nm also able to be distinguished.

Investigation of the 6 p 2(3 P 0) n p Rydberg series of bismuth by multiphoton excitation

NASA Astrophysics Data System (ADS)

Bühler, B.; Cremer, C.; Gerber, G.

1985-03-01

Rydberg states of the odd-parity series 6 p 2(3 p 0) n p of BiI are excited by a three-photon process. A two-photon dissociation of Bi2 into excited atomic states followed by a one-photon absorption leads to highly excited atomic Rydberg states up to n = 32. States of the even-parity Rydberg series 6 p 2(3 p 0) nsJ=1/2, ndJ=3/2 and ndJ=5/2 are also observed. In order to avoid the background caused by ionization of the bismuth molecules we performed a two-color excitation with pulsed dye lasers. With this experiment the 6 p 2(3 p 0) npJ=3/2 Rydberg series could be resolved up to n=75. The increasing quantum defect of this series is due to a perturbing state close to the first ionization limit. By a MQDT analysis we obtain the energy of the perturbing state and a value of 58,761.68±0.1 cm-1 for the first ionization limit of atomic bismuth.

Engineering Photon-Photon Interactions within Rubidium-Filled Waveguides

NASA Astrophysics Data System (ADS)

Perrella, C.; Light, P. S.; Vahid, S. Afshar; Benabid, F.; Luiten, A. N.

2018-04-01

Strong photon-photon interactions are a required ingredient for deterministic two-photon optical quantum logic gates. Multiphoton transitions in dense atomic vapors have been shown to be a promising avenue for producing such interactions. The strength of a multiphoton interaction can be enhanced by conducting the interaction in highly confined geometries such as small-cross-section optical waveguides. We demonstrate, both experimentally and theoretically, that the strength of such interactions scale only with the optical mode diameter, d , not d2 as might be initially expected. This weakening of the interaction arises from atomic motion inside the waveguides. We create an interaction between two optical signals, at 780 and 776 nm, using the 5 S1 /2→5 D5 /2 two-photon transition in rubidium vapor within a range of hollow-core fibers with different core sizes. The interaction strength is characterized by observing the absorption and phase shift induced on the 780-nm beam, which is in close agreement with theoretical modeling that accounts for the atomic motion inside the fibers. These observations demonstrate that transit-time effects upon multiphoton transitions are of key importance when engineering photon-photon interactions within small-cross-section waveguides that might otherwise be thought to lead to enhanced optical nonlinearity through increased intensities.

Study of clusters using negative ion photodetachment spectroscopy

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

Zhao, Yuexing

1995-12-01

The weak van der Waals interaction between an open-shell halogen atom and a closed-shell atom or molecule has been investigated using zero electron kinetic energy (ZEKE) spectroscopy. This technique is also applied to study the low-lying electronic states in GaAs and GaAs -. In addition, the spectroscopy and electron detachment dynamics of several small carbon cluster anions are studied using resonant multiphoton detachment spectroscopy.

Multiphoton laser ionization for energy conversion in barium vapor

NASA Astrophysics Data System (ADS)

Makdisi, Y.; Kokaj, J.; Afrousheh, K.; Mathew, J.; Nair, R.; Pichler, G.

2013-03-01

We have studied the ion detection of barium atoms in special heated ovens with a tungsten rod in the middle of the stainless steel tube. The tungsten rod was heated indirectly by the oven body heaters. A bias voltage between the cell body and the tungsten rod of 9 V was used to collect electrons, after the barium ions had been created. However, we could collect the electrons even without the bias voltage, although with ten times less efficiency. We studied the conditions for the successful bias-less thermionic signal detection using excimer/dye laser two-photon excitation of Rydberg states below and above the first ionization limit (two-photon wavelength at 475.79 nm). We employed a hot-pipe oven and heat-pipe oven (with inserted mesh) in order to generate different barium vapor distributions inside the oven. The thermionic signal increased by a factor of two under heat-pipe oven conditions.

Second generation measurement of the electric dipole moment of the electron using trapped ThF+ ions

NASA Astrophysics Data System (ADS)

Ng, Kia Boon; Zhou, Yan; Gresh, Daniel; Cairncross, William; Grau, Matthew; Ni, Yiqi; Ye, Jun; Cornell, Eric

2016-05-01

ThF+ has been chosen as the candidate for a second generation measurement of the electric dipole moment of the electron (eEDM). Compared to the current HfF+ eEDM experiment, ThF+ has several advantages: (i) the eEDM-sensitive state (3Δ1) is the ground state, which facilitates a long coherence time; (ii) its effective electric field (38 GV/cm) is 50% larger than that of HfF+, which promises a direct increase of the eEDM sensitivity; and (iii) the ionization energy of neutral ThF is lower than its dissociation energy, which introduces greater flexibility in rotational state-selective photoionization via core-nonpenetrating Rydberg states. Here, we present progress of our experimental setup, preliminary spectroscopic data of multi-photon ionization, and discussions of new features in ion trapping, state preparation and population readout.

Artificial plasma cusp generated by upper hybrid instabilities in HF heating experiments at HAARP

NASA Astrophysics Data System (ADS)

Kuo, Spencer; Snyder, Arnold

2013-05-01

High Frequency Active Auroral Research Program digisonde was operated in a fast mode to record ionospheric modifications by the HF heating wave. With the O mode heater of 3.2 MHz turned on for 2 min, significant virtual height spread was observed in the heater off ionograms, acquired beginning the moment the heater turned off. Moreover, there is a noticeable bump in the virtual height spread of the ionogram trace that appears next to the plasma frequency (~ 2.88 MHz) of the upper hybrid resonance layer of the HF heating wave. The enhanced spread and the bump disappear in the subsequent heater off ionograms recorded 1 min later. The height distribution of the ionosphere in the spread situation indicates that both electron density and temperature increases exceed 10% over a large altitude region (> 30 km) from below to above the upper hybrid resonance layer. This "mini cusp" (bump) is similar to the cusp occurring in daytime ionograms at the F1-F2 layer transition, indicating that there is a small ledge in the density profile reminiscent of F1-F2 layer transitions. Two parametric processes exciting upper hybrid waves as the sidebands by the HF heating waves are studied. Field-aligned purely growing mode and lower hybrid wave are the respective decay modes. The excited upper hybrid and lower hybrid waves introduce the anomalous electron heating which results in the ionization enhancement and localized density ledge. The large-scale density irregularities formed in the heat flow, together with the density irregularities formed through the parametric instability, give rise to the enhanced virtual height spread. The results of upper hybrid instability analysis are also applied to explain the descending feature in the development of the artificial ionization layers observed in electron cyclotron harmonic resonance heating experiments.

Analysis of chirality by femtosecond laser ionization mass spectrometry.

PubMed

Horsch, Philipp; Urbasch, Gunter; Weitzel, Karl-Michael

2012-09-01

Recent progress in the field of chirality analysis employing laser ionization mass spectrometry is reviewed. Emphasis is given to femtosecond (fs) laser ionization work from the author's group. We begin by reviewing fundamental aspects of determining circular dichroism (CD) in fs-laser ionization mass spectrometry (fs-LIMS) discussing an example from the literature (resonant fs-LIMS of 3-methylcyclopentanone). Second, we present new data indicating CD in non-resonant fs-LIMS of propylene oxide. Copyright © 2012 Wiley Periodicals, Inc., A Wiley Company.

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

Ghosh Deb, S.; Sinha, C.; Chattopadhyay, A.

The modification in the dynamics of the electron-impact ionization process of a Li{sup +} ion due to an intense linearly polarized monochromatic laser field (n{gamma}e,2e) is studied theoretically using coplanar geometry. Significant laser modifications are noted due to multiphoton effects both in the shape and magnitude of the triple-differential cross sections (TDCSs) with respect to the field-free (FF) situation. The net effect of the laser field is to suppress the FF cross sections in the zeroth-order approximation [Coulomb-Volkov (CV)] of the ejected electron wave function, while in the first order [modified Coulomb-Volkov (MCV)], the TDCSs are found to be enhancedmore » or suppressed depending on the kinematics of the process. The strong FF recoil dominance for the (e,2e) process of an ionic target at low incident energy is destroyed in the presence of the laser field. The FF binary-to-recoil ratio changes remarkably in the presence of the laser field, particularly at low incident energies. The difference between the multiphoton CV and the FF results indicates that for the ionic target, the Kroll-Watson sum rule does not hold well at the present energy range in contrast to the neutral atom (He) case. The TDCSs are found to be quite sensitive with respect to the initial phase of the laser field, particularly at higher incident energies. A significant qualitative difference is noted in the multiphoton ejected energy distribution (double-differential cross sections) between the CV and the MCV models. Variation of the TDCSs with respect to the laser phase is also studied.« less

Enhanced Axial Resolution of Wide-Field Two-Photon Excitation Microscopy by Line Scanning Using a Digital Micromirror Device.

PubMed

Park, Jong Kang; Rowlands, Christopher J; So, Peter T C

2017-01-01

Temporal focusing multiphoton microscopy is a technique for performing highly parallelized multiphoton microscopy while still maintaining depth discrimination. While the conventional wide-field configuration for temporal focusing suffers from sub-optimal axial resolution, line scanning temporal focusing, implemented here using a digital micromirror device (DMD), can provide substantial improvement. The DMD-based line scanning temporal focusing technique dynamically trades off the degree of parallelization, and hence imaging speed, for axial resolution, allowing performance parameters to be adapted to the experimental requirements. We demonstrate this new instrument in calibration specimens and in biological specimens, including a mouse kidney slice.

Enhanced Axial Resolution of Wide-Field Two-Photon Excitation Microscopy by Line Scanning Using a Digital Micromirror Device

PubMed Central

Park, Jong Kang; Rowlands, Christopher J.; So, Peter T. C.

2017-01-01

Temporal focusing multiphoton microscopy is a technique for performing highly parallelized multiphoton microscopy while still maintaining depth discrimination. While the conventional wide-field configuration for temporal focusing suffers from sub-optimal axial resolution, line scanning temporal focusing, implemented here using a digital micromirror device (DMD), can provide substantial improvement. The DMD-based line scanning temporal focusing technique dynamically trades off the degree of parallelization, and hence imaging speed, for axial resolution, allowing performance parameters to be adapted to the experimental requirements. We demonstrate this new instrument in calibration specimens and in biological specimens, including a mouse kidney slice. PMID:29387484

Bombyx mori silk protein films microprocessing with a nanosecond ultraviolet laser and a femtosecond laser workstation: theory and experiments

NASA Astrophysics Data System (ADS)

Lazare, S.; Sionkowska, A.; Zaborowicz, M.; Planecka, A.; Lopez, J.; Dijoux, M.; Louména, C.; Hernandez, M.-C.

2012-01-01

Laser microprocessing of several biopolymers from renewable resources is studied. Three proteinic materials were either extracted from the extracellular matrix like Silk Fibroin/Sericin and collagen, or coming from a commercial source like gelatin. All can find future applications in biomedical experimentation, in particular for cell scaffolding. Films of ˜hundred of microns thick were made by aqueous solution drying and laser irradiation. Attention is paid to the properties making them processable with two laser sources: the ultraviolet and nanosecond (ns) KrF (248 nm) excimer and the infrared and femtosecond (fs) Yb:KGW laser. The UV radiation is absorbed in a one-photon resonant process to yield ablation and the surface foaming characteristics of a laser-induced pressure wave. To the contrary, resonant absorption of the IR photons of the fs laser is not possible and does not take place. However, the high field of the intense I>˜1012 W/cm2 femtosecond laser pulse ionizes the film by the multiphoton absorption followed by the electron impact mechanism, yielding a dense plasma capable to further absorb the incident radiation of the end of the pulse. The theoretical model of this absorption is described in detail, and used to discuss the presented experimental effects (cutting, ablation and foaming) of the fs laser. The ultraviolet laser was used to perform simultaneous multiple spots experiments in which energetic foaming yields melt ejection and filament spinning. Airborne nanosize filaments "horizontally suspended by both ends" (0.25 μm diameter and 10 μm length) of silk biopolymer were observed upon irradiation with large fluences.

Resonance-assisted decay of nondispersive wave packets.

PubMed

Wimberger, Sandro; Schlagheck, Peter; Eltschka, Christopher; Buchleitner, Andreas

2006-07-28

We present a quantitative semiclassical theory for the decay of nondispersive electronic wave packets in driven, ionizing Rydberg systems. Statistically robust quantities are extracted combining resonance-assisted tunneling with subsequent transport across chaotic phase space and a final ionization step.

Resonance ionization for analytical spectroscopy

DOEpatents

Hurst, George S.; Payne, Marvin G.; Wagner, Edward B.

1976-01-01

This invention relates to a method for the sensitive and selective analysis of an atomic or molecular component of a gas. According to this method, the desired neutral component is ionized by one or more resonance photon absorptions, and the resultant ions are measured in a sensitive counter. Numerous energy pathways are described for accomplishing the ionization including the use of one or two tunable pulsed dye lasers.

Numerical calculation of nonlinear ultrashort laser pulse propagation in transparent Kerr media

NASA Astrophysics Data System (ADS)

Arnold, Cord L.; Heisterkamp, Alexander; Ertmer, Wolfgang; Lubatschowski, Holger

2005-03-01

In the focal region of tightly focused ultrashort laser pulses, sufficient high intensities to initialize nonlinear ionization processes are easily achieved. Due to these nonlinear ionization processes, mainly multiphoton ionization and cascade ionization, free electrons are generated in the focus resulting in optical breakdown. A model including both nonlinear pulse propagation and plasma generation is used to calculate numerically the interaction of ultrashort pulses with their self-induced plasma in the vicinity of the focus. The model is based on a (3+1)-dimensional nonlinear Schroedinger equation describing the pulse propagation coupled to a system of rate equations covering the generation of free electrons. It is applicable to any transparent Kerr medium, whose linear and nonlinear optical parameters are known. Numerical calculations based on this model are used to understand nonlinear side effects, such as streak formation, occurring in addition to optical breakdown during short pulse refractive eye surgeries like fs-LASIK. Since the optical parameters of water are a good first-order approximation to those of corneal tissue, water is used as model substance. The free electron density distribution induced by focused ultrashort pulses as well as the pulses spatio-temporal behavior are studied in the low-power regime around the critical power for self-focusing.

Investigating Atmospheric Oxidation with Molecular Dynamics Imaging and Spectroscopy

NASA Astrophysics Data System (ADS)

Merrill, W. G.; Case, A. S.; Keutsch, F. N.

2013-06-01

Volatile organic compounds (VOCs) in the Earth's atmosphere constitute trace gas species emitted primarily from the biosphere, and are the subject of inquiry for a variety of air quality and climate studies. Reactions intiated (primarily) by the hydroxyl radical (OH) lead to a myriad of oxygenated species (OVOCs), which in turn are prone to further oxidation. Investigations of the role that VOC oxidation plays in tropospheric chemistry have brought to light two troubling scenarios: (1) VOCs are responsible in part for the production of two EPA-regulated pollutants---tropospheric ozone and organic aerosol---and (2) the mechanistic details of VOC oxidation remain convoluted and poorly understood. The latter issue hampers the implementation of near-explicit atmospheric simulations, and large discrepancies in OH reactivity exist between measurements and models at present. Such discrepancies underscore the need for a more thorough description of VOC oxidation. Time-of-flight measurements and ion-imaging techniques are viable options for resolving some of the mechanistic and energetic details of VOC oxidation. Molecular beam studies have the advantage of foregoing unwanted bimolecular reactions, allowing for the characterization of specific processes which must typically compete with the complex manifold of VOC oxidation pathways. The focus of this work is on the unimolecular channels of organic peroxy radical intermediates, which are necessarily generated during VOC oxidation. Such intermediates may isomerize and decompose into distinct chemical channels, enabling the unambiguous detection of each pathway. For instance, a (1 + 1') resonance enhanced multiphoton ionization (REMPI) scheme may be employed to detect carbon monoxide generated from a particular unimolecular process. A number of more subtle mechanistic details may be explored as well. By varying the mean free path of the peroxy radicals in a flow tube, the role of collisional quenching in these unimolecular channels can be assessed. Reactive species may also be introduced to explore the competition between bimolecular and unimolecular pathways. Vibrational modes may also be excited by an IR laser, providing insight about the role of vibrational mediation in VOC oxidation.

Spectroscopy of Lithium Atoms and Molecules on Helium Nanodroplets

PubMed Central

2013-01-01

We report on the spectroscopic investigation of lithium atoms and lithium dimers in their triplet manifold on the surface of helium nanodroplets (HeN). We present the excitation spectrum of the 3p ← 2s and 3d ← 2s two-photon transitions for single Li atoms on HeN. The atoms are excited from the 2S(Σ) ground state into Δ, Π, and Σ pseudodiatomic molecular substates. Excitation spectra are recorded by resonance enhanced multiphoton ionization time-of-flight (REMPI-TOF) mass spectroscopy, which allows an investigation of the exciplex (Li*–Hem, m = 1–3) formation process in the Li–HeN system. Electronic states are shifted and broadened with respect to free atom states, which is explained within the pseudodiatomic model. The assignment is assisted by theoretical calculations, which are based on the Orsay–Trento density functional where the interaction between the helium droplet and the lithium atom is introduced by a pairwise additive approach. When a droplet is doped with more than one alkali atom, the fragility of the alkali–HeN systems leads preferably to the formation of high-spin molecules on the droplets. We use this property of helium nanodroplets for the preparation of Li dimers in their triplet ground state (13Σu+). The excitation spectrum of the 23Πg(ν′ = 0–11) ← 13Σu+(ν″ = 0) transition is presented. The interaction between the molecule and the droplet manifests in a broadening of the transitions with a characteristic asymmetric form. The broadening extends to the blue side of each vibronic level, which is caused by the simultaneous excitation of the molecule and vibrations of the droplet (phonons). The two isotopes of Li form 6Li2 and 7Li2 as well as isotope mixed 6Li7Li molecules on the droplet surface. By using REMPI-TOF mass spectroscopy, isotope-dependent effects could be studied. PMID:23895106

Ultraviolet photodissociation dynamics of the n-propyl and i-propyl radicals

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

Song, Yu; Zheng, Xianfeng; Zhou, Weidong

2015-06-14

Ultraviolet (UV) photodissociation dynamics of jet-cooled n-propyl (n-C{sub 3}H{sub 7}) radical via the 3s Rydberg state and i-propyl (i-C{sub 3}H{sub 7}) radical via the 3p Rydberg states are studied in the photolysis wavelength region of 230–260 nm using high-n Rydberg atom time-of-flight and resonance enhanced multiphoton ionization techniques. The H-atom photofragment yield spectra of the n-propyl and i-propyl radicals are broad and in good agreement with the UV absorption spectra. The H + propene product translational energy distributions, P(E{sub T})’s, of both n-propyl and i-propyl are bimodal, with a slow component peaking around 5-6 kcal/mol and a fast one peakingmore » at ∼50 kcal/mol (n-propyl) and ∼45 kcal/mol (i-propyl). The fraction of the average translational energy in the total excess energy, 〈f{sub T}〉, is 0.3 for n-propyl and 0.2 for i-propyl, respectively. The H-atom product angular distributions of the slow components of n-propyl and i-propyl are isotropic, while that of the fast component of n-propyl is anisotropic (with an anisotropy parameter ∼0.8) and that of i-propyl is nearly isotropic. Site-selective loss of the β hydrogen atom is confirmed using the partially deuterated CH{sub 3}CH{sub 2}CD{sub 2} and CH{sub 3}CDCH{sub 3} radicals. The bimodal translational energy and angular distributions indicate two dissociation pathways to the H + propene products in the n-propyl and i-propyl radicals: (i) a unimolecular dissociation pathway from the hot ground-state propyl after internal conversion from the 3s and 3p Rydberg states and (ii) a direct, prompt dissociation pathway coupling the Rydberg excited states to a repulsive part of the ground-state surface, presumably via a conical intersection.« less

Physicochemical Processes on Ice Dust Towards Deuterium Enrichment

NASA Astrophysics Data System (ADS)

Watanabe, Naoki

2017-06-01

Water and some organic molecules were found to be deuterium enriched toward various astronomical targets. Understanding the deuterium-fractionation process pertains directly to know how and when molecules are created. Although gas phase chemistry is certainly important for deuterium enrichment, the role of physicochemical processes on the dust surfaces should be also considered. In fact, the extreme deuterium enrichment of formaldehyde and methanol requires the dust grain-surface process. In this context, we have performed a series of experiments on the formation of deuterated species of water and simple organic molecules. From the results of these experiments and related works, I will discuss the key processes for the deuterium enrichment on dust. For deuterium chemistry, another important issue is the ortho-to-para ratio (OPR) of H_{2}, which is closely related to the formation of H_{2}D^{+} and thus the deuterium fractionation of molecules in the gas phase. Because the radiative nuclear spin conversion of H_{2} is forbidden, the ortho-para conversion is very slow in the gas phase. In contrast, it was not obvious how the nuclear spins behave on cosmic dust. Therefore, it is desirable to understand how the OPR of H_{2} is determined on the dust surfaces. We have tackled this issue experimentally. Using experimental techniques of molecular beam, photostimulated-desorption, and resonance-enhanced multiphoton ionization, we measured the OPRs of H_{2} photodesorbed from amorphous solid water at around 10 K, which is an ice dust analogue. It was first demonstrated that the rate of spin conversion from ortho to para drastically increases from 2.4 × 10^{-4} to 1.7 × 10^{-3} s^{-1} within the very narrow temperature window of 9.2 to16 K. The observed strong temperature cannot be explained by solely state-mixing models ever proposed but by the energy dissipation model via two phonon process. I will present our recent experiments regarding this.

Development of Terahertz Rayleigh Scattering Diagnostics for a Solid Rocket Exhaust Plume

DTIC Science & Technology

2010-10-28

experiment. Many of these experiments involve a diagnostic of a plasma which while different from strictly particles, still provides insight into the...investigate the properties of small plasma objects. Their study developed a method that could be used as a diagnostic for small scale plasmas such...as laser sparks, avalanche-streamer transitions, and resonance-enhanced multi- photon ionizations processes. They treated a plasma as a source of

Nonlinear structured-illumination enhanced temporal focusing multiphoton excitation microscopy with a digital micromirror device

PubMed Central

Cheng, Li-Chung; Lien, Chi-Hsiang; Da Sie, Yong; Hu, Yvonne Yuling; Lin, Chun-Yu; Chien, Fan-Ching; Xu, Chris; Dong, Chen Yuan; Chen, Shean-Jen

2014-01-01

In this study, the light diffraction of temporal focusing multiphoton excitation microscopy (TFMPEM) and the excitation patterning of nonlinear structured-illumination microscopy (NSIM) can be simultaneously and accurately implemented via a single high-resolution digital micromirror device. The lateral and axial spatial resolutions of the TFMPEM are remarkably improved through the second-order NSIM and projected structured light, respectively. The experimental results demonstrate that the lateral and axial resolutions are enhanced from 397 nm to 168 nm (2.4-fold) and from 2.33 μm to 1.22 μm (1.9-fold), respectively, in full width at the half maximum. Furthermore, a three-dimensionally rendered image of a cytoskeleton cell featuring ~25 nm microtubules is improved, with other microtubules at a distance near the lateral resolution of 168 nm also able to be distinguished. PMID:25136483

Precise control of atomic nitrogen production in an electron cyclotron resonance plasma using N2/noble gas mixtures

NASA Astrophysics Data System (ADS)

Fan, Z. Y.; Newman, N.

1998-07-01

The atomic nitrogen flux and impacting ion kinetic energy are two important parameters which influence the quality of deposited nitride films using reactive growth. In this letter, a method is described to control the flux and kinetic energy of atomic and molecular nitrogen ions using an electron cyclotron resonance plasma with N2/Ar and N2/Ne gas mixtures. The results clearly show that the addition of neon to nitrogen plasma can remarkably enhance the production rate of atomic nitrogen due to Penning ionization involving the metastable state of Ne. In contrast, the addition of argon significantly decreases the rate.

Energy partitioning in polyatomic chemical reactions: Quantum state resolved studies of highly exothermic atom abstraction reactions from molecules in the gas phase and at the gas-liquid interface

NASA Astrophysics Data System (ADS)

Zolot, Alexander M.

This thesis recounts a series of experiments that interrogate the dynamics of elementary chemical reactions using quantum state resolved measurements of gas-phase products. The gas-phase reactions F + HCl → HF + Cl and F + H2O → HF + OH are studied using crossed supersonic jets under single collision conditions. Infrared (IR) laser absorption probes HF product with near shot-noise limited sensitivity and high resolution, capable of resolving rovibrational states and Doppler lineshapes. Both reactions yield inverted vibrational populations. For the HCl reaction, strongly bimodal rotational distributions are observed, suggesting microscopic branching of the reaction mechanism. Alternatively, such structure may result from a quantum-resonance mediated reaction similar to those found in the well-characterized F + HD system. For the H2O reaction, a small, but significant, branching into v = 2 is particularly remarkable because this manifold is accessible only via the additional center of mass collision energy in the crossed jets. Rotationally hyperthermal HF is also observed. Ab initio calculations of the transition state geometry suggest mechanisms for both rotational and vibrational excitation. Exothermic chemical reaction dynamics at the gas-liquid interface have been investigated by colliding a supersonic jet of F atoms with liquid squalane (C30H62), a low vapor pressure hydrocarbon compatible with the high vacuum environment. IR spectroscopy provides absolute HF( v,J) product densities and Doppler resolved velocity component distributions perpendicular to the surface normal. Compared to analogous gas-phase F + hydrocarbon reactions, the liquid surface is a more effective "heat sink," yet vibrationally excited populations reveal incomplete thermal accommodation with the surface. Non-Boltzmann J-state populations and hot Doppler lineshapes that broaden with HF excitation indicate two competing scattering mechanisms: (i) a direct reactive scattering channel, whereby newly formed molecules leave the surface without equilibrating, and (ii) a partially accommodated fraction that shares vibrational, rotational, and translational energy with the liquid surface before returning to the gas phase. Finally, a velocity map ion imaging apparatus has been implemented to investigate reaction dynamics in crossed molecular beams. Resonantly enhanced multiphoton ionization (REMPI) results in rotational, vibrational, and electronic state selectivity. Velocity map imaging measurements provide differential cross sections and information about the internal energy distribution of the undetected collision partner.

Metastable States Arising from the Ablation of Solid Copper

NASA Astrophysics Data System (ADS)

Andrejeva, Anna; Harris, Joe; Wright, Tim

2014-06-01

Laser ablation is a popular method for generating metal atoms so that metal clusters, complexes, and molecules may be investigated in gas phase spectroscopic studies. However, the initial production of a highly energetic metal plasma from the surface of a solid metal target can produce atoms which are not in their ground electronic state, and consequently atomic spectra can become quite complicated due to transitions arising from metastable atomic excited states which remain populated on the experimental timescale. Presented herein are details of the laser vaporisation source in use by our group. Spectra of atomic copper are presented, recorded via (1+1') and (2+1) resonance enhanced multiphoton ionisation (REMPI) spectroscopy. The energetic regions examined are expected to correspond to the (4s24p) 2P ← 2S and the (4s2nd) 2D ← 2S Rydberg series respectively, but the observed spectra also exhibit many additional contributions which are found to arise from electronically excited states, and these will be discussed.

Unravelling the dynamical origin of below- and near-threshold harmonic generation of H 2 + in an intense NIR laser field

DOE PAGES

Heslar, John; Chu, Shih-I.

2016-11-24

Recently, the study of near- and below- threshold regime harmonics as a potential source of intense coherent vacuum-ultraviolet radiation has received considerable attention. However, the dynamical origin of these lower harmonics, particularly for the molecular systems, is less understood and largely unexplored. Here we perform the first fully ab initio and high precision 3D quantum study of the below- and near-threshold harmonic generation of H 2 + molecules in an intense 800-nm near-infrared (NIR) laser field. Furthermore, combining with a synchrosqueezing transform of the quantum time-frequency spectrum and an extended semiclassical analysis, we explore in-depth the roles of various quantummore » trajectories, including short- and long trajectories, multiphoton trajectories, resonance-enhanced trajectories, and multiple rescattering trajectories of the below- and near- threshold harmonic generation processes. Our results shed new light on the dynamical origin of the below- and near-threshold harmonic generation and various quantum trajectories for diatomic molecules for the first time.« less

Real-time observation of cascaded electronic relaxation processes in p-Fluorotoluene

NASA Astrophysics Data System (ADS)

Hao, Qiaoli; Deng, Xulan; Long, Jinyou; Wang, Yanmei; Abulimiti, Bumaliya; Zhang, Bing

2017-08-01

Ultrafast electronic relaxation processes following two photoexcitation of 400 nm in p-Fluorotoluene (pFT) have been investigated utilizing time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Cascaded electronic relaxation processes started from the electronically excited S2 state are directly imaged in real time and well characterized by two distinct time constants of 85 ± 10 fs and 2.4 ± 0.3 ps. The rapid component corresponds to the lifetime of the initially excited S2 state, including the structure relaxation from the Franck-Condon region to the conical intersection of S2/S1 and the subsequent internal conversion to the highly excited S1 state. While, the slower relaxation constant is attributed to the further internal conversion to the high levels of S0 from the secondarily populated S1 locating in the channel three region. Moreover, dynamical differences with benzene and toluene of analogous structures, including, specifically, the slightly slower relaxation rate of S2 and the evidently faster decay of S1, are also presented and tentatively interpreted as the substituent effects. In addition, photoelectron kinetic energy and angular distributions reveal the feature of accidental resonances with low-lying Rydberg states (the 3p, 4s and 4p states) during the multi-photon ionization process, providing totally unexpected but very interesting information for pFT.

Tunable Spectrum Selectivity for Multiphoton Absorption with Enhanced Visible Light Trapping in ZnO Nanorods.

PubMed

Tan, Kok Hong; Lim, Fang Sheng; Toh, Alfred Zhen Yang; Zheng, Xia-Xi; Dee, Chang Fu; Majlis, Burhanuddin Yeop; Chai, Siang-Piao; Chang, Wei Sea

2018-04-17

Observation of visible light trapping in zinc oxide (ZnO) nanorods (NRs) correlated to the optical and photoelectrochemical properties is reported. In this study, ZnO NR diameter and c-axis length respond primarily at two different regions, UV and visible light, respectively. ZnO NR diameter exhibits UV absorption where large ZnO NR diameter area increases light absorption ability leading to high efficient electron-hole pair separation. On the other hand, ZnO NR c-axis length has a dominant effect in visible light resulting from a multiphoton absorption mechanism due to light reflection and trapping behavior in the free space between adjacent ZnO NRs. Furthermore, oxygen vacancies and defects in ZnO NRs are associated with the broad visible emission band of different energy levels also highlighting the possibility of the multiphoton absorption mechanism. It is demonstrated that the minimum average of ZnO NR c-axis length must satisfy the linear regression model of Z p,min = 6.31d to initiate the multiphoton absorption mechanism under visible light. This work indicates the broadening of absorption spectrum from UV to visible light region by incorporating a controllable diameter and c-axis length on vertically aligned ZnO NRs, which is important in optimizing the design and functionality of electronic devices based on light absorption mechanism. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Infrared Multiphoton Dissociation for Quantitative Shotgun Proteomics

PubMed Central

Ledvina, Aaron R.; Lee, M. Violet; McAlister, Graeme C.; Westphall, Michael S.; Coon, Joshua J.

2012-01-01

We modified a dual-cell linear ion trap mass spectrometer to perform infrared multiphoton dissociation (IRMPD) in the low pressure trap of a dual-cell quadrupole linear ion trap (dual cell QLT) and perform large-scale IRMPD analyses of complex peptide mixtures. Upon optimization of activation parameters (precursor q-value, irradiation time, and photon flux), IRMPD subtly, but significantly outperforms resonant excitation CAD for peptides identified at a 1% false-discovery rate (FDR) from a yeast tryptic digest (95% confidence, p = 0.019). We further demonstrate that IRMPD is compatible with the analysis of isobaric-tagged peptides. Using fixed QLT RF amplitude allows for the consistent retention of reporter ions, but necessitates the use of variable IRMPD irradiation times, dependent upon precursor mass-to-charge (m/z). We show that IRMPD activation parameters can be tuned to allow for effective peptide identification and quantitation simultaneously. We thus conclude that IRMPD performed in a dual-cell ion trap is an effective option for the large-scale analysis of both unmodified and isobaric-tagged peptides. PMID:22480380

Dynamical origin of near- and below-threshold harmonic generation of Cs in an intense mid-infrared laser field.

PubMed

Li, Peng-Cheng; Sheu, Yae-Lin; Laughlin, Cecil; Chu, Shih-I

2015-05-20

Near- and below-threshold harmonic generation provides a potential approach to generate vacuum-ultraviolet frequency comb. However, the dynamical origin of in these lower harmonics is less understood and largely unexplored. Here we perform an ab initio quantum study of the near- and below-threshold harmonic generation of caesium (Cs) atoms in an intense 3,600-nm mid-infrared laser field. Combining with a synchrosqueezing transform of the quantum time-frequency spectrum and an extended semiclassical analysis, the roles of multiphoton and multiple rescattering trajectories on the near- and below-threshold harmonic generation processes are clarified. We find that the multiphoton-dominated trajectories only involve the electrons scattered off the higher part of the combined atom-field potential followed by the absorption of many photons in near- and below-threshold regime. Furthermore, only the near-resonant below-threshold harmonic is exclusive to exhibit phase locked features. Our results shed light on the dynamic origin of the near- and below-threshold harmonic generation.

Multiphoton, confocal, and lifetime microscopy for molecular imaging in cartilage

NASA Astrophysics Data System (ADS)

Wachsmann-Hogiu, Sebastian; Krakow, Deborah; Kirilova, Veneta T.; Cohn, Daniel H.; Bertolotto, Cristina; Acuna, Dora; Fang, Qiyin; Krivorov, Nikola; Farkas, Daniel L.

2005-03-01

It has recently been shown that mutations in Filamin A and B genes produce a large spectrum of skeletal disorders in developing fetuses. However, high-resolution optical microscopy in cartilage growth plate using fluorescent antibody assays, which should elucidate molecular aspects of these disorders, is extremely difficult due to the high level of autofluoresce in this tissue. We apply multiphoton, confocal, lifetime and spectral microscopy to (i) image and characterize autofluorophores in chondrocytes and subtract their contributions to obtain a corrected antibody-marker fluorescence signal, and (ii) measure the interaction between Filamin A and B proteins by detecting the fluorescence resonance energy transfer (FRET) between markers of the two proteins. Taking advantage of the different fluorescence spectra of the endogenous and exogenous markers, we can significantly reduce the autofluorescence background. Preliminary results of the FRET experiments suggest no interaction between Filamin A and B proteins. However, developing of new antibodies targeting the carboxy-terminal immunoglobulin-like domain may be necessary to confirm this result.

Femtosecond two-photon Rabi oscillations in excited He driven by ultrashort intense laser fields

NASA Astrophysics Data System (ADS)

Fushitani, M.; Liu, C.-N.; Matsuda, A.; Endo, T.; Toida, Y.; Nagasono, M.; Togashi, T.; Yabashi, M.; Ishikawa, T.; Hikosaka, Y.; Morishita, T.; Hishikawa, A.

2016-02-01

Coherent light-matter interaction provides powerful methods for manipulating quantum systems. Rabi oscillation is one such process. As it enables complete population transfer to a target state, it is thus routinely exploited in a variety of applications in photonics, notably quantum information processing. The extension of coherent control techniques to the multiphoton regime offers wider applicability, and access to highly excited or dipole-forbidden transition states. However, the multiphoton Rabi process is often disrupted by other competing nonlinear effects such as the a.c. Stark shift, especially at the high laser-field intensities necessary to achieve ultrafast Rabi oscillations. Here we demonstrate a new route to drive two-photon Rabi oscillations on timescales as short as tens of femtoseconds, by utilizing the strong-field phenomenon known as Freeman resonance. The scenario is not specific to atomic helium as investigated in the present study, but broadly applicable to other systems, thus opening new prospects for the ultrafast manipulation of Rydberg states.

Insight into plant cell wall chemistry and structure by combination of multiphoton microscopy with Raman imaging.

PubMed

Heiner, Zsuzsanna; Zeise, Ingrid; Elbaum, Rivka; Kneipp, Janina

2018-04-01

Spontaneous Raman scattering microspectroscopy, second harmonic generation (SHG) and 2-photon excited fluorescence (2PF) were used in combination to characterize the morphology together with the chemical composition of the cell wall in native plant tissues. As the data obtained with unstained sections of Sorghum bicolor root and leaf tissues illustrate, nonresonant as well as pre-resonant Raman microscopy in combination with hyperspectral analysis reveals details about the distribution and composition of the major cell wall constituents. Multivariate analysis of the Raman data allows separation of different tissue regions, specifically the endodermis, xylem and lumen. The orientation of cellulose microfibrils is obtained from polarization-resolved SHG signals. Furthermore, 2-photon autofluorescence images can be used to image lignification. The combined compositional, morphological and orientational information in the proposed coupling of SHG, Raman imaging and 2PF presents an extension of existing vibrational microspectroscopic imaging and multiphoton microscopic approaches not only for plant tissues. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An ultrafast nanotip electron gun triggered by grating-coupled surface plasmons

NASA Astrophysics Data System (ADS)

Schröder, Benjamin; Sivis, Murat; Bormann, Reiner; Schäfer, Sascha; Ropers, Claus

2015-12-01

We demonstrate multiphoton photoelectron emission from gold nanotips induced by nanofocusing surface plasmons, resonantly excited on the tip shaft by a grating coupler. The tip is integrated into an electron gun assembly, which facilitates control over the spatial emission sites and allows us to disentangle direct grating emission from plasmon-triggered apex emission. The nanoscale source size of this electron gun concept enables highly coherent electron pulses with applications in ultrafast electron imaging and diffraction.

An ultrafast nanotip electron gun triggered by grating-coupled surface plasmons

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

Schröder, Benjamin; Sivis, Murat; Bormann, Reiner

We demonstrate multiphoton photoelectron emission from gold nanotips induced by nanofocusing surface plasmons, resonantly excited on the tip shaft by a grating coupler. The tip is integrated into an electron gun assembly, which facilitates control over the spatial emission sites and allows us to disentangle direct grating emission from plasmon-triggered apex emission. The nanoscale source size of this electron gun concept enables highly coherent electron pulses with applications in ultrafast electron imaging and diffraction.

Transverse magnetic field effect on the giant Goos–Hänchen shifts based on a degenerate two-level system

NASA Astrophysics Data System (ADS)

Nasehi, R.

2018-06-01

We study the effect of the Goos–Hänchen (GH) shifts through a cavity with degenerate two-level systems in the line of . For this purpose, we focus on the transverse magnetic field (TMF) in a Floquet frame to obtain the giant GH shifts. Physically, the collisional effects of TMF lead to increasing the population trapping in the ground state. However, we demonstrate that the population trapping generates the large negative or positive GH shifts and simultaneously switches from superluminal to subluminal (or vice versa). Also, we investigate the other optical properties such as the longitudinal magnetic field (LMF), which plays an important role in the control of the GH shifts and leads to the generation of new subsystems. In the next step, we evaluate the GH shifts beyond the multi-photon resonance condition by the control of TMF. Moreover, we compute the appearance of negative and positive GH shifts by setting the width of the incident Gaussian beams in the presence of a multi-photon resonance condition. Our results show that superluminal or subluminal light propagation can be simultaneously controlled by adjusting the rates of the TMF and LMF. The significant effects of these factors on the degenerate two-level systems provide different applications such as slow light, optical switches and quantum information storage.

Exact steady state of a Kerr resonator with one- and two-photon driving and dissipation: Controllable Wigner-function multimodality and dissipative phase transitions

NASA Astrophysics Data System (ADS)

Bartolo, Nicola; Minganti, Fabrizio; Casteels, Wim; Ciuti, Cristiano

2016-09-01

We present exact results for the steady-state density matrix of a general class of driven-dissipative systems consisting of a nonlinear Kerr resonator in the presence of both coherent (one-photon) and parametric (two-photon) driving and dissipation. Thanks to the analytical solution, obtained via the complex P -representation formalism, we are able to explore any regime, including photon blockade, multiphoton resonant effects, and a mesoscopic regime with large photon density and quantum correlations. We show how the interplay between one- and two-photon driving provides a way to control the multimodality of the Wigner function in regimes where the semiclassical theory exhibits multistability. We also study the emergence of dissipative phase transitions in the thermodynamic limit of large photon numbers.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory.

PubMed

Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J; Lopata, Kenneth

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory

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

Sissay, Adonay; Abanador, Paul; Mauger, François

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagatingmore » the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.« less

New resonances from the coherence of Auger and intercoulombic (ICD) processes in the photoionization of endohedral fullerenes

NASA Astrophysics Data System (ADS)

Chakraborty, Himadri; Wise, Jacob; de, Ruma; Javani, Mohammad; Manson, Steve; Madjet, Mohamed

2014-05-01

Considering the photoionization of Ar@C60 , we predict resonant femtosecond decays of both Ar and C60 vacancies through the continua of atom-fullerene hybrid final states. The resulting resonances emerge from the interference between simultaneous autoionizing and intercoulombic decay (ICD) processes. For Ar 3s --> np excitations, these resonances are far stronger than the Ar-to-C60 resonant ICDs, while for C60 excitations they are strikingly larger than the corresponding Auger features. The results indicate the power of hybridization to enhance decay rates, and modify lifetimes and line profiles. These decays are also likely to exist generally in the ionization of molecules, nano-dimers and -polymers, and fullerene onions that support hybridized electrons as well. A jellium based time-dependent local density approximation (TDLDA), with the Leeuwen and Baerends exchange-correlation functional to produce accurate asymptotic behavior, is employed to calculate the dynamical response of the system to the photon field.

Disentangling formation of multiple-core holes in aminophenol molecules exposed to bright X-FEL radiation

NASA Astrophysics Data System (ADS)

Zhaunerchyk, V.; Kamińska, M.; Mucke, M.; Squibb, R. J.; Eland, J. H. D.; Piancastelli, M. N.; Frasinski, L. J.; Grilj, J.; Koch, M.; McFarland, B. K.; Sistrunk, E.; Gühr, M.; Coffee, R. N.; Bostedt, C.; Bozek, J. D.; Salén, P.; Meulen, P. v. d.; Linusson, P.; Thomas, R. D.; Larsson, M.; Foucar, L.; Ullrich, J.; Motomura, K.; Mondal, S.; Ueda, K.; Richter, R.; Prince, K. C.; Takahashi, O.; Osipov, T.; Fang, L.; Murphy, B. F.; Berrah, N.; Feifel, R.

2015-12-01

Competing multi-photon ionization processes, some leading to the formation of double core hole states, have been examined in 4-aminophenol. The experiments used the linac coherent light source (LCLS) x-ray free electron laser, in combination with a time-of-flight magnetic bottle electron spectrometer and the correlation analysis method of covariance mapping. The results imply that 4-aminophenol molecules exposed to the focused x-ray pulses of the LCLS sequentially absorb more than two x-ray photons, resulting in the formation of multiple core holes as well as in the sequential removal of photoelectrons and Auger electrons (so-called PAPA sequences).

Disentangling formation of multiple-core holes in aminophenol molecules exposed to bright X-FEL radiation

DOE PAGES

Zhaunerchyk, V.; Kaminska, M.; Mucke, M.; ...

2015-10-28

Competing multi-photon ionization processes, some leading to the formation of double core hole states, have been examined in 4-aminophenol. The experiments used the linac coherent light source (LCLS) x-ray free electron laser, in combination with a time-of-flight magnetic bottle electron spectrometer and the correlation analysis method of covariance mapping. Furthermore, the results imply that 4-aminophenol molecules exposed to the focused x-ray pulses of the LCLS sequentially absorb more than two x-ray photons, resulting in the formation of multiple core holes as well as in the sequential removal of photoelectrons and Auger electrons (so-called PAPA sequences).

Tuning excitation laser wavelength for secondary resonance in low-intensity phase-selective laser-induced breakdown spectroscopy for in-situ analytical measurement of nanoaerosols

NASA Astrophysics Data System (ADS)

Xiong, Gang; Li, Shuiqing; Tse, Stephen D.

2018-02-01

In recent years, a novel low-intensity phase-selective laser-induced breakdown spectroscopy (PS-LIBS) technique has been developed for unique elemental-composition identification of aerosolized nanoparticles, where only the solid-phase nanoparticles break down, forming nanoplasmas, without any surrounding gas-phase breakdown. Additional work has demonstrated that PS-LIBS emissions can be greatly enhanced with secondary resonant excitation by matching the excitation laser wavelength with an atomic transition line in the formed nanoplasma, thereby achieving low limits of detection. In this work, a tunable dye laser is employed to investigate the effects of excitation wavelength and irradiance on in-situ PS-LIBS measurements of TiO2 nanoaerosols. The enhancement factor by resonant excitation can be 220 times greater than that for non-resonant cases under similar conditions. Moreover, the emitted spectra are unique for the selected resonant transition lines for a given element, suggesting the potential to make precise phase-selective and analyte-selective measurements of nanoparticles in a multicomponent multiphase system. The enhancement factor by resonant excitation is highly sensitive to excitation laser wavelength, with narrow excitation spectral windows, i.e., 0.012 to 0.023 nm (FWHM, full width at half maximum) for Ti (I) neutral atomic lines, and 0.051 to 0.139 nm (FWHM) for Ti (II) single-ionized atomic lines. Boltzmann analysis of the emission intensities, temporal response of emissions, and emission dependence on excitation irradiance are investigated to understand aspects of the generated nanoplasmas such as temperature, local thermodynamic equilibrium (LTE), and excitation mechanism.

Diode-laser-based RIMS measurements of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1998-12-01

Double- and triple-resonance excitation schemes for the ionization of strontium are presented. Use of single-mode diode lasers for the resonance excitations provides a high degree of optical isotopic selectivity: with double-resonance, selectivity of >104 for 90Sr against the stable Sr isotopes has been demonstrated. Measurement of lineshapes and stable isotope shifts in the triple-resonance process indicate that optical selectivity should increase to ˜109. When combined with mass spectrometer selectivity this is sufficient for measurement of 90Sr at background environmental levels. Additionally, autoionizing resonances have been investigated for improving ionization efficiency with lower power lasers.

Ultra-violet avalanche photodiode based on AlN/GaN periodically-stacked-structure

NASA Astrophysics Data System (ADS)

Wu, Xingzhao; Zheng, Jiyuan; Wang, Lai; Brault, Julien; Matta, Samuel; Hao, Zhibiao; Sun, Changzheng; Xiong, Bing; Luo, Yi; Han, Yianjun; Wang, Jian; Li, Hongtao; Khalfioui, Mohamed A.; Li, Mo; Kang, Jianbin; Li, Qian

2018-02-01

The high-gain photomultiplier tube (PMT) is the most popular method to detect weak ultra-violet signals which attenuate quickly in atmosphere, although the vacuum tube makes it fragile and difficult to integrate. To overcome the disadvantage of PMT, an AlN/GaN periodically-stacked-structure (PSS) avalanche photodiode (APD) has been proposed, finally achieving good quality of high gain and low excessive noise. As there is a deep g valley only in the conduction band of both GaN and AlN, the electron transfers suffering less scattering and thus becomes easier to obtain the threshold of ionization impact. Because of unipolar ionization in the PSS APD, it works in linear mode. Four prototype devices of 5-period, 10-period, 15-period, and 20-period were fabricated to verify that the gain of APD increases exponentially with period number. And in 20-period device, a recorded high and stable gain of 104 was achieved under constant bias. In addition, it is proved both experimentally and theoretically, that temperature stability on gain is significantly improved in PSS APD. And it is found that the resonant enhancement in interfacial ionization may bring significant enhancement of electron ionization performance. To make further progress in PSS APD, the device structure is investigated by simulation. Both the gain and temperature stability are optimized alternatively by a proper design of periodical thickness and AlN layer occupancy.

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

Fu, H.B.; Hu, Y.J.; Bernstein, E.R.

Small methanol clusters are formed by expanding a mixture of methanol vapor seeded in helium and are detected using vacuum UV (vuv) (118 nm) single-photon ionization/linear time-of-flight mass spectrometer (TOFMS). Protonated cluster ions, (CH{sub 3}OH){sub n-1}H{sup +} (n=2-8), formed through intracluster ion-molecule reactions following ionization, essentially correlate to the neutral clusters, (CH{sub 3}OH){sub n}, in the present study using 118 nm light as the ionization source. Both experimental and Born-Haber calculational results clarify that not enough excess energy is released into protonated cluster ions to initiate further fragmentation in the time scale appropriate for linear TOFMS. Size-specific spectra for (CH{submore » 3}OH){sub n} (n=4 to 8) clusters in the OH stretch fundamental region are recorded by IR+vuv (118 nm) nonresonant ion-dip spectroscopy through the detection chain of IR multiphoton predissociation and subsequent vuv single-photon ionization. The general structures and gross features of these cluster spectra are consistent with previous theoretical calculations. The lowest-energy peak contributed to each cluster spectrum is redshifted with increasing cluster size from n=4 to 8, and limits near {approx}3220 cm{sup -1} in the heptamer and octamer. Moreover, IR+vuv nonresonant ionization detected spectroscopy is employed to study the OH stretch first overtone of the methanol monomer. The rotational temperature of the clusters is estimated to be at least 50 K based on the simulation of the monomer rotational envelope under clustering conditions.« less

Femtosecond laser three-dimensional micro- and nanofabrication

NASA Astrophysics Data System (ADS)

Sugioka, Koji; Cheng, Ya

2014-12-01

The rapid development of the femtosecond laser has revolutionized materials processing due to its unique characteristics of ultrashort pulse width and extremely high peak intensity. The short pulse width suppresses the formation of a heat-affected zone, which is vital for ultrahigh precision fabrication, whereas the high peak intensity allows nonlinear interactions such as multiphoton absorption and tunneling ionization to be induced in transparent materials, which provides versatility in terms of the materials that can be processed. More interestingly, irradiation with tightly focused femtosecond laser pulses inside transparent materials makes three-dimensional (3D) micro- and nanofabrication available due to efficient confinement of the nonlinear interactions within the focal volume. Additive manufacturing (stereolithography) based on multiphoton absorption (two-photon polymerization) enables the fabrication of 3D polymer micro- and nanostructures for photonic devices, micro- and nanomachines, and microfluidic devices, and has applications for biomedical and tissue engineering. Subtractive manufacturing based on internal modification and fabrication can realize the direct fabrication of 3D microfluidics, micromechanics, microelectronics, and photonic microcomponents in glass. These microcomponents can be easily integrated in a single glass microchip by a simple procedure using a femtosecond laser to realize more functional microdevices, such as optofluidics and integrated photonic microdevices. The highly localized multiphoton absorption of a tightly focused femtosecond laser in glass can also induce strong absorption only at the interface of two closely stacked glass substrates. Consequently, glass bonding can be performed based on fusion welding with femtosecond laser irradiation, which provides the potential for applications in electronics, optics, microelectromechanical systems, medical devices, microfluidic devices, and small satellites. This review paper describes the concepts and principles of femtosecond laser 3D micro- and nanofabrication and presents a comprehensive review on the state-of-the-art, applications, and the future prospects of this technology.

Femtosecond laser three-dimensional micro- and nanofabrication

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

Sugioka, Koji, E-mail: ksugioka@riken.jp; Cheng, Ya, E-mail: ya.cheng@siom.ac.cn

2014-12-15

The rapid development of the femtosecond laser has revolutionized materials processing due to its unique characteristics of ultrashort pulse width and extremely high peak intensity. The short pulse width suppresses the formation of a heat-affected zone, which is vital for ultrahigh precision fabrication, whereas the high peak intensity allows nonlinear interactions such as multiphoton absorption and tunneling ionization to be induced in transparent materials, which provides versatility in terms of the materials that can be processed. More interestingly, irradiation with tightly focused femtosecond laser pulses inside transparent materials makes three-dimensional (3D) micro- and nanofabrication available due to efficient confinement ofmore » the nonlinear interactions within the focal volume. Additive manufacturing (stereolithography) based on multiphoton absorption (two-photon polymerization) enables the fabrication of 3D polymer micro- and nanostructures for photonic devices, micro- and nanomachines, and microfluidic devices, and has applications for biomedical and tissue engineering. Subtractive manufacturing based on internal modification and fabrication can realize the direct fabrication of 3D microfluidics, micromechanics, microelectronics, and photonic microcomponents in glass. These microcomponents can be easily integrated in a single glass microchip by a simple procedure using a femtosecond laser to realize more functional microdevices, such as optofluidics and integrated photonic microdevices. The highly localized multiphoton absorption of a tightly focused femtosecond laser in glass can also induce strong absorption only at the interface of two closely stacked glass substrates. Consequently, glass bonding can be performed based on fusion welding with femtosecond laser irradiation, which provides the potential for applications in electronics, optics, microelectromechanical systems, medical devices, microfluidic devices, and small satellites. This review paper describes the concepts and principles of femtosecond laser 3D micro- and nanofabrication and presents a comprehensive review on the state-of-the-art, applications, and the future prospects of this technology.« less

An investigation on 800 nm femtosecond laser ablation of K9 glass in air and vacuum

NASA Astrophysics Data System (ADS)

Xu, Shi-zhen; Yao, Cai-zhen; Dou, Hong-qiang; Liao, Wei; Li, Xiao-yang; Ding, Ren-jie; Zhang, Li-juan; Liu, Hao; Yuan, Xiao-dong; Zu, Xiao-tao

2017-06-01

Ablation rates of K9 glass were studied as a function of femtosecond laser fluences. The central wavelength was 800 nm, and pulse durations of 35 fs and 500 fs in air and vacuum were employed. Ablation thresholds of 0.42 J/cm2 and 2.1 J/cm2 were obtained at 35 fs and 500 fs, respectively, which were independent with the ambient conditions and depend on the incident pulse numbers due to incubation effects. The ablation rate of 35 fs pulse laser increased with the increasing of laser fluence in vacuum, while in air condition, it slowly increased to a plateau at high fluence. The ablation rate of 500 fs pulse laser showed an increase at low fluence and a slow drop of ablation rate was observed at high fluence in air and vacuum, which may due to the strong defocusing effects associated with the non-equilibrium ionization of air, and/or the shielding effects of conduction band electrons (CBEs) produced by multi-photon ionization and impact ionization in K9 glass surface. The typical ablation morphologies, e.g. smooth zone and laser-induced periodic surface structures (LIPSS) were also presented and illustrated.

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

Sturm, F. P.; Tong, X. M.; Palacios, A.

Here, we used ultrashort femtosecond vacuum ultraviolet (VUV) and infrared (IR) pulses in a pump-probe scheme to map the dynamics and nonequilibrium dissociation channels of excited neutral H 2 molecules. A nuclear wave packet is created in the B 1Σmore » $$+\\atop{u}$$ state of the neutral H 2 molecule by absorption of the ninth harmonic of the driving infrared laser field. Due to the large stretching amplitude of the molecule excited in the B 1Σ$$+\\atop{u}$$ electronic state, the effective H 2 + ionization potential changes significantly as the nuclear wave packet vibrates in the bound, highly electronically and vibrationally excited B potential-energy curve. We probed such dynamics by ionizing the excited neutral molecule using time-delayed VUV-or-IR radiation. We identified the nonequilibrium dissociation channels by utilizing three-dimensional momentum imaging of the ion fragments. We also found that different dissociation channels can be controlled, to some extent, by changing the IR laser intensity and by choosing the wavelength of the probe laser light. Furthermore, we concluded that even in a benchmark molecular system such as H 2*, the interpretation of the nonequilibrium multiphoton and multicolor ionization processes is still a challenging task, requiring intricate theoretical analysis.« less

Setup and use of a two-laser multiphoton microscope for multichannel intravital fluorescence imaging

PubMed Central

Entenberg, David; Wyckoff, Jeffrey; Gligorijevic, Bojana; Roussos, Evanthia T; Verkhusha, Vladislav V; Pollard, Jeffrey W; Condeelis, John

2014-01-01

Characterizing biological mechanisms dependent upon the interaction of many cell types in vivo requires both multiphoton microscope systems capable of expanding the number and types of fluorophores that can be imaged simultaneously while removing the wavelength and tunability restrictions of existing systems, and enhanced software for extracting critical cellular parameters from voluminous 4D data sets. We present a procedure for constructing a two-laser multiphoton microscope that extends the wavelength range of excitation light, expands the number of simultaneously usable fluorophores and markedly increases signal to noise via ‘over-clocking’ of detection. We also utilize a custom-written software plug-in that simplifies the quantitative tracking and analysis of 4D intravital image data. We begin by describing the optics, hardware, electronics and software required, and finally the use of the plug-in for analysis. We demonstrate the use of the setup and plug-in by presenting data collected via intravital imaging of a mouse model of breast cancer. The procedure may be completed in ~24 h. PMID:21959234

Design, fabrication and characterization of rugged, high-performance quantum dot photocathodes

NASA Astrophysics Data System (ADS)

Pietryga, Jeffrey; Robel, Istvan; Makarov, Nikolay; Lim, Jaehoon; Lin, Qianglu; Lewellen, John; Moody, Nathan

Semiconductor nanocrystal quantum dots (QDs) are bright, tunable fluorophores used as, e.g., biolabels and downcoverting phosphors. Such applications make use of over three decades in advances in techniques for overcoming the natural tendency of these materials toward losing photoexcited carriers to surface defect states or to ionization. Ironically, QDs first gained attention as a material class for use in photocatalysis, which uses QD photoionization to drive redox reactions. Here, we explore the use of QDs in an alternative application that also exploits photoionization, namely within photocathodes for the electron guns that will enable next-generation light sources. We evaluate the efficiency of electron photoemission of conductive, solution-cast QD films of a variety of compositions in a typical electron gun configuration. By quantifying photocurrent as a function of excitation photon energy, excitation intensity and pulse duration, we demonstrate efficiencies superior to standard copper cathodes in films that are more robust against oxidation. Finally, we establish the dominant mechanism responsible for electron emission in the multi-photon excitation regime, which suggests numerous pathways for further enhancements. We gratefully acknowledge the support of the Los Alamos National Laboratory Directed Research and Development (LDRD) program.

A Near-Threshold Shape Resonance in the Valence-Shell Photoabsorption of Linear Alkynes

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

Jacovella, U.; Holland, D. M. P.; Boyé-Péronne, S.

2015-12-17

The room-temperature photoabsorption spectra of a number of linear alkynes with internal triple bonds (e.g., 2-butyne, 2-pentyne, and 2- and 3-hexyne) show similar resonances just above the lowest ionization threshold of the neutral molecules. These features result in a substantial enhancement of the photoabsorption cross sections relative to the cross sections of alkynes with terminal triple bonds (e.g., propyne, 1-butyne, 1-pentyne,...). Based on earlier work on 2-butyne [Xu et al., J. Chem. Phys. 2012, 136, 154303], these features are assigned to excitation from the neutral highest occupied molecular orbital (HOMO) to a shape resonance with g (l = 4) charactermore » and approximate pi symmetry. This generic behavior results from the similarity of the HOMOs in all internal alkynes, as well as the similarity of the corresponding g pi virtual orbital in the continuum. Theoretical calculations of the absorption spectrum above the ionization threshold for the 2- and 3-alkynes show the presence of a shape resonance when the coupling between the two degenerate or nearly degenerate pi channels is included, with a dominant contribution from l = 4. These calculations thus confirm the qualitative arguments for the importance of the l = 4 continuum near threshold for internal alkynes, which should also apply to other linear internal alkynes and alkynyl radicals. The 1-alkynes do not have such high partial waves present in the shape resonance. The lower l partial waves in these systems are consistent with the broader features observed in the corresponding spectra.« less

Resonant ionization spectroscopy of autoionizing Rydberg states in cobalt and redetermination of its ionization potential

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

Liu, Yuan; Gottwald, T.; Mattolat, C.

We obtained multi-step resonance ionization spectroscopy of cobalt using a hot-cavity laser ion source and three Ti:Sapphire lasers. Furthermore, the photoionization spectra revealed members of five new autoionizing Rydberg series that originate from three different lower levels of 3d 74s5s h 4F 9/2, 3d 74s4d f 4G 11/2, and 3d 74s4d f 4H 13/2 and converge to the first four excited states of singly ionized Co. Our analyses of the Rydberg series yield 63564.689 0.036 cm -1 as the first ionization potential of Co, which is an order of magnitude more accurate than the previous estimation. Using a three-step resonancemore » ionization scheme that employs an autoinizing Rydberg state in the last transition, we obtained an overall ionization efficiency of about 18% for Co.« less

Resonant ionization spectroscopy of autoionizing Rydberg states in cobalt and redetermination of its ionization potential

DOE PAGES

Liu, Yuan; Gottwald, T.; Mattolat, C.; ...

2017-03-20

We obtained multi-step resonance ionization spectroscopy of cobalt using a hot-cavity laser ion source and three Ti:Sapphire lasers. Furthermore, the photoionization spectra revealed members of five new autoionizing Rydberg series that originate from three different lower levels of 3d 74s5s h 4F 9/2, 3d 74s4d f 4G 11/2, and 3d 74s4d f 4H 13/2 and converge to the first four excited states of singly ionized Co. Our analyses of the Rydberg series yield 63564.689 0.036 cm -1 as the first ionization potential of Co, which is an order of magnitude more accurate than the previous estimation. Using a three-step resonancemore » ionization scheme that employs an autoinizing Rydberg state in the last transition, we obtained an overall ionization efficiency of about 18% for Co.« less

SALI chemical analysis of provided samples

NASA Technical Reports Server (NTRS)

Becker, Christopher H.

1993-01-01

SRI has completed the chemical analysis of all the samples supplied by NASA. The final batch of four samples consisted of: one inch diameter MgF2 mirror, control 1200-ID-FL3; one inch diameter neat resin, PMR-15, AO171-IV-55, half exposed and half unexposed; one inch diameter chromic acid anodized, EOIM-3 120-47 aluminum disc; and AO-exposed and unexposed samples of fullerene extract material in powdered form, pressed into In foil for analysis. Chemical analyses of the surfaces were performed by the surface analysis by laser ionization (SALI) method. The analyses emphasize surface contamination or general organic composition. SALI uses nonselective photoionization of sputtered or desorbed atoms and molecules above but close (approximately one mm) to the surface, followed by time-of-flight (TOF) mass spectrometry. In these studies, we used laser-induced desorption by 5-ns pulse-width 355-nm light (10-100 mJ/sq cm) and single-photon ionization (SPI) by coherent 118-nm radiation (at approximately 5 x 10(exp 5) W/sq cm). SPI was chosen primarily for its ability to obtain molecular information, whereas multiphoton ionization (not used in the present studies) is intended primarily for elemental and small molecule information. In addition to these four samples, the Au mirror (EOIM-3 200-11, sample four) was depth profiled again. Argon ion sputtering was used together with photoionization with intense 355-nm radiation (35-ps pulsewidths). Depth profiles are similar to those reported earlier, showing reproducibility. No chromium was found in the sample above noise level; its presence could at most be at the trace level. Somewhat more Ni appears to be present in the Au layer in the unexposed side, indicating thermal diffusion without chemical enhancement. The result of the presence of oxygen is apparently to tie-up/draw out the Ni as an oxide at the surface. The exposed region has a brownish tint appearance to the naked eye.

Transition-matrix theory for two-photon ionization of rare-gas atoms and isoelectronic ions with application to argon

NASA Astrophysics Data System (ADS)

Starace, Anthony F.; Jiang, Tsin-Fu

1987-08-01

A transition-matrix theory for two-photon ionization processes in rare-gas atoms or isoelectronic ions is presented. Uncoupled ordinary differential equations are obtained for the radial functions needed to calculate the two-photon transition amplitude. The implications of these equations are discussed in detail. In particular, the role of correlations involving virtually excited electron pairs, which are known to be essential to the description of single-photon processes, is examined for multiphoton ionization processes. Additionally, electron scattering interactions between two electron-hole pairs are introduced into our transition amplitude in the boson approximation since these have been found important in two-photon ionization of xenon by L'Huillier and Wendin [J. Phys. B 20, L37 (1987)]. Application of our theory is made to two-photon ionization of the 3p subshell of argon below the one-photon ionization threshold. Our results are compared to previous calculations of McGuire [Phys. Rev. A 24, 835 (1981)], of Moccia, Rahman, and Rizzo [J. Phys. B 16, 2737 (1983)], and of Pindzola and Kelly [Phys. Rev. A 11, 1543 (1975)]. Results are presented for both circularly and linearly polarized photons. Among our findings are, firstly, that the electron scattering interactions, which have not been included in previous calculations for argon, produce a substantial reduction in the two-photon single-ionization cross section below the one-photon ionization threshold, which is in agreement with findings of L'Huillier and Wendin for xenon. Secondly, we find that de-excitation of virtually excited electron pairs by absorption of a photon is important for describing the interaction of the atom with the photon field, as in the case of single-photon ionization processes, but that further excitation of virtually excited electron pairs by the photon field has completely negligible effects, indicating a major simplification of the theory for higher-order absorption processes.

Alignment, orientation, and Coulomb explosion of difluoroiodobenzene studied with the pixel imaging mass spectrometry (PImMS) camera.

PubMed

Amini, Kasra; Boll, Rebecca; Lauer, Alexandra; Burt, Michael; Lee, Jason W L; Christensen, Lauge; Brauβe, Felix; Mullins, Terence; Savelyev, Evgeny; Ablikim, Utuq; Berrah, Nora; Bomme, Cédric; Düsterer, Stefan; Erk, Benjamin; Höppner, Hauke; Johnsson, Per; Kierspel, Thomas; Krecinic, Faruk; Küpper, Jochen; Müller, Maria; Müller, Erland; Redlin, Harald; Rouzée, Arnaud; Schirmel, Nora; Thøgersen, Jan; Techert, Simone; Toleikis, Sven; Treusch, Rolf; Trippel, Sebastian; Ulmer, Anatoli; Wiese, Joss; Vallance, Claire; Rudenko, Artem; Stapelfeldt, Henrik; Brouard, Mark; Rolles, Daniel

2017-07-07

Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (C 6 H 3 F 2 I) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with a pixel imaging mass spectrometry camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one-and three-dimensional alignment and mixed-field orientation and compare the Coulomb explosion process induced at both wavelengths.

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

Photochemical Ignition Studies. 3. Ignition by Efficient and Resonant Multiphoton Photochemical Formation of Microplasmas

DTIC Science & Technology

1987-06-01

Fragments," Chem. Phys., Vol. 33, p. 161, 1978. 5. R.C. Sausa, A.J. Alfano , and A.W. Miziolek, "ArF Laser Photoproduction and Sensitive Detection of Carbon...Unlversity/APL Chemical Propulsion I Purdue University Information Agency Department of Chomistry ATTN: TW. Christian ATTN: H. Grant Johns Hopkins...of Chemistry ATTN: T.W. Christian ATTN: E. Grant Johns Hopkins Road West Lafayette, IN 47906 Laurel, MD 20707 2 Purdue University University of

Broken selection rule in the quantum Rabi model

PubMed Central

Forn-Díaz, P.; Romero, G.; Harmans, C. J. P. M.; Solano, E.; Mooij, J. E.

2016-01-01

Understanding the interaction between light and matter is very relevant for fundamental studies of quantum electrodynamics and for the development of quantum technologies. The quantum Rabi model captures the physics of a single atom interacting with a single photon at all regimes of coupling strength. We report the spectroscopic observation of a resonant transition that breaks a selection rule in the quantum Rabi model, implemented using an LC resonator and an artificial atom, a superconducting qubit. The eigenstates of the system consist of a superposition of bare qubit-resonator states with a relative sign. When the qubit-resonator coupling strength is negligible compared to their own frequencies, the matrix element between excited eigenstates of different sign is very small in presence of a resonator drive, establishing a sign-preserving selection rule. Here, our qubit-resonator system operates in the ultrastrong coupling regime, where the coupling strength is 10% of the resonator frequency, allowing sign-changing transitions to be activated and, therefore, detected. This work shows that sign-changing transitions are an unambiguous, distinctive signature of systems operating in the ultrastrong coupling regime of the quantum Rabi model. These results pave the way to further studies of sign-preserving selection rules in multiqubit and multiphoton models. PMID:27273346

Birth of a resonant attosecond wavepacket

NASA Astrophysics Data System (ADS)

Argenti, L.; Gruson, V.; Barreau, L.; Jimenez-Galan, A.; Risoud, F.; Caillat, J.; Maquet, A.; Carre, B.; Lepetit, F.; Hergott, J.-F.; Ruchon, T.; Taieb, R.; Martin, F.; Salieres, P.

2016-05-01

Both amplitude and phase are needed to characterize the dynamics of a wavepacket. However, such characterization is difficult when both attosecond and femtosecond timescales are involved, as it is the case for broadband photoionization to a continuum encompassing autoionizing states. Here we demonstrate that Rainbow RABBIT, a new attosecond interferometry, allows the measurement of amplitude and phase of a photoelectron wavepacket created through a Fano resonance with unprecedented precision. In the experiment, a tunable attosecond pulse train is combined with the fundamental laser pulse to induce two-photon transitions in helium via an intermediate autoionizing state. From the energy and time-delay resolved signal, we fully reconstruct the resonant electron wavepacket as it builds up in the continuum. Measurements accurately match the predictions of a new time-resolved multi-photon resonant model, known to reproduce ab initio calculations. This agreement confirms the potential of Rainbow RABBIT to investigate photoemission delays in ultrafast processes governed by electron correlation, as well as to control structured electron wavepackets. now at Univ. Central Florida, Orlando, FL (USA).

Numerical Studies of Optimization and Aberration Correction Methods for the Preliminary Demonstration of the Parametric Ionization Cooling (PIC) Principle in the Twin Helix Muon Cooling Channel

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

Maloney, J. A.; Morozov, V. S.; Derbenev, Ya. S.

Muon colliders have been proposed for the next generation of particle accelerators that study high-energy physics at the energy and intensity frontiers. In this paper we study a possible implementation of muon ionization cooling, Parametric-resonance Ionization Cooling (PIC), in the twin helix channel. The resonant cooling method of PIC offers the potential to reduce emittance beyond that achievable with ionization cooling with ordinary magnetic focusing. We examine optimization of a variety of parameters, study the nonlinear dynamics in the twin helix channel and consider possible methods of aberration correction.

COMPACT NON-CONTACT TOTAL EMISSION DETECTION FOR IN-VIVO MULTI-PHOTON EXCITATION MICROSCOPY

PubMed Central

Glancy, Brian; Karamzadeh, Nader S.; Gandjbakhche, Amir H.; Redford, Glen; Kilborn, Karl; Knutson, Jay R.; Balaban, Robert S.

2014-01-01

Summary We describe a compact, non-contact design for a Total Emission Detection (c-TED) system for intra-vital multi-photon imaging. To conform to a standard upright two-photon microscope design, this system uses a parabolic mirror surrounding a standard microscope objective in concert with an optical path that does not interfere with normal microscope operation. The non-contact design of this device allows for maximal light collection without disrupting the physiology of the specimen being examined. Tests were conducted on exposed tissues in live animals to examine the emission collection enhancement of the c-TED device compared to heavily optimized objective-based emission collection. The best light collection enhancement was seen from murine fat (5×-2× gains as a function of depth), while murine skeletal muscle and rat kidney showed gains of over two and just under two-fold near the surface, respectively. Gains decreased with imaging depth (particularly in the kidney). Zebrafish imaging on a reflective substrate showed close to a two-fold gain throughout the entire volume of an intact embryo (approximately 150 μm deep). Direct measurement of bleaching rates confirmed that the lower laser powers (enabled by greater light collection efficiency) yielded reduced photobleaching in vivo. The potential benefits of increased light collection in terms of speed of imaging and reduced photo-damage, as well as the applicability of this device to other multi-photon imaging methods is discussed. PMID:24251437

Study of Auger effect in DNA when bound to molecules containing platinum. A possible application to hadrontherapy

NASA Astrophysics Data System (ADS)

Kobayashi, K.; Usami, N.; Sasaki, I.; Frohlich, H.; Le Sech, C.

2003-01-01

Complexes made of DNA and Cyclo-Pt bound to plasmid DNA, were placed in aqueous solution and irradiated with monochromatic X-rays in the range E=8.5-13 keV, including the resonant photoabsorption energy of the L III shell of the platinum atom. The number of single- and double-strand breaks (ssb and dsb) induced by irradiation on a supercoiled DNA plasmid was measured by the production of circular-nicked and linear forms. In order to disentangle the contribution of the direct effects imparted to ionization, and the indirect effects due to a free radical attack, experiments have been performed in the presence of a small concentration (64 mmol l -1) of hydroxyl free radical scavenger dimethyl sulfoxide (DMSO). An enhancement of the number of ssb and dsb is observed when the plasmids contain the Pt intercalating molecules. Even when off-resonant X-rays are used, the strand break efficiency remains higher than expected based upon the absorption cross-section, as if the Pt bound to DNA is increasing the yield of strand breaks. A mechanism is suggested, involving photoelectrons generated from the ionization of water which efficiently ionize Pt atoms. This observation may provide an insight to understanding the effects of new radiotherapy protocols, associated chemotherapeutic agents such as cisplatin and ordinary radiotherapy for tumoral treatments.

Temporal focusing-based multiphoton excitation microscopy via digital micromirror device.

PubMed

Yih, Jenq-Nan; Hu, Yvonne Yuling; Sie, Yong Da; Cheng, Li-Chung; Lien, Chi-Hsiang; Chen, Shean-Jen

2014-06-01

This Letter presents an enhanced temporal focusing-based multiphoton excitation (MPE) microscope in which the conventional diffraction grating is replaced by a digital micromirror device (DMD). Experimental results from imaging a thin fluorescence film show that the 4.0 μm axial resolution of the microscope is comparable with that of a setup incorporating a 600  lines/mm grating; hence, the optical sectioning ability of the proposed setup is demonstrated. Similar to a grating, the DMD diffracts illuminating light frequencies for temporal focusing; additionally, it generates arbitrary patterns. Since the DMD is placed on the image-conjugate plane of the objective lens' focal plane, the MPE pattern can be projected on the focal plane precisely.

Propagation of intense short laser pulses in the atmosphere.

PubMed

Sprangle, P; Peñano, J R; Hafizi, B

2002-10-01

The propagation of short, intense laser pulses in the atmosphere is investigated theoretically and numerically. A set of three-dimensional (3D), nonlinear propagation equations is derived, which includes the effects of dispersion, nonlinear self-focusing, stimulated molecular Raman scattering, multiphoton and tunneling ionization, energy depletion due to ionization, relativistic focusing, and ponderomotively excited plasma wakefields. The instantaneous frequency spread along a laser pulse in air, which develops due to various nonlinear effects, is analyzed and discussed. Coupled equations for the power, spot size, and electron density are derived for an intense ionizing laser pulse. From these equations we obtain an equilibrium for a single optical-plasma filament, which involves a balancing between diffraction, nonlinear self-focusing, and plasma defocusing. The equilibrium is shown to require a specific distribution of power along the filament. It is found that in the presence of ionization a self-guided optical filament is not realizable. A method for generating a remote spark in the atmosphere is proposed, which utilizes the dispersive and nonlinear properties of air to cause a low-intensity chirped laser pulse to compress both longitudinally and transversely. For optimally chosen parameters, we find that the transverse and longitudinal focal lengths can be made to coincide, resulting in rapid intensity increase, ionization, and white light generation in a localized region far from the source. Coupled equations for the laser spot size and pulse duration are derived, which can describe the focusing and compression process in the low-intensity regime. More general examples involving beam focusing, compression, ionization, and white light generation near the focal region are studied by numerically solving the full set of 3D, nonlinear propagation equations.

Preliminary Work for Identifying and Tracking Combustion Reaction Pathways by Coherent Microwave Mapping of Photoelectrons

DTIC Science & Technology

2016-06-24

wall Radar technique has been built and preliminary results of pyrolysis of iso-butane have been obtained. Qualitative measurements of ethylene in...The (2+1) REMPI ionizations of ethylene (C2H4, 11B3u(π,3p) Rydberg manifold) was selectively induced at 310─325nm. The ethylene was detectable at...quantitative measurements of ethylene as one of the pyrolysis products by using coherent microwave Rayleigh scattering (Radar) from Resonant Enhanced Multi

A High Pressure Pulsed Expansion Valve for Gases, Liquids, and Supercritical Fluids

NASA Astrophysics Data System (ADS)

Köster, C.; Grotemeyer, J.; Schlag, E. W.

1990-12-01

A novel design of a pulsed valve for coupling chromatographic techniques with gaseous and liquid mobile phases to a time-of-flight mass spectrometer with multiphoton ionization (MUPI) is presented. The valve can be operated in low pressure regions ( <10 bar) up to temperatures of 350 °C and at higher pressures (300 bar) up to temperatures of 200 °C. Pulse widths lower than 100 μs could be measured. First results demonstrate the ability of interfacing of liquid chromatography to MUPI-mass spectrometry. Additional coupling of CO2-laser desorption to the valve allows the interface to be used for mass spectrometric measurements of nonvolatile biomolecules.

Spatially resolved organic analysis of the Allende meteorite

NASA Technical Reports Server (NTRS)

Zenobi, Renato; Philippoz, Jean-Michel; Zare, Richard N.; Buseck, Peter R.

1989-01-01

The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende meteorite has been probed with two-step laser desorption/laser multiphoton ionization mass spectrometry. This method allows direct in situ analysis with a spatial resolution of 1 sq mm or better of selected organic molecules. Spectra from freshly fractured interior surfaces of the meteorite show that PAH concentrations are locally high compared to the average concentrations found by wet chemical analysis of pulverized samples. The data suggest that the PAHs are primarily associated with the fine-grained matrix, where the organic polymer occurs. In addition, highly substituted PAH skeletons were observed. Interiors of individual chondrules were devoid of PAHs at the detection limit (about 0.05 ppm).

Resonance ionization laser ion sources for on-line isotope separators (invited).

PubMed

Marsh, B A

2014-02-01

A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states. For many radioactive ion beam experiments, laser resonance ionization is the only means of achieving an acceptable level of beam purity without compromising isotope yield. Furthermore, by performing element selection at the location of the ion source, the propagation of unwanted radioactivity downstream of the target assembly is reduced. Whilst advances in laser technology have improved the performance and reliability of laser ion sources and broadened the range of suitable commercially available laser systems, many recent developments have focused rather on the laser/atom interaction region in the quest for increased selectivity and/or improved spectral resolution. Much of the progress in this area has been achieved by decoupling the laser ionization from competing ionization processes through the use of a laser/atom interaction region that is physically separated from the target chamber. A new application of gas catcher laser ion source technology promises to expand the capabilities of projectile fragmentation facilities through the conversion of otherwise discarded reaction fragments into high-purity low-energy ion beams. A summary of recent RILIS developments and the current status of laser ion sources worldwide is presented.

Measurement of absorption spectrum of deuterium oxide (D{sub 2}O) and its application to signal enhancement in multiphoton microscopy at the 1700-nm window

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

Wang, Yuxin; Wen, Wenhui; Wang, Kai

2016-01-11

1700-nm window has been demonstrated to be a promising excitation window for deep-tissue multiphoton microscopy (MPM). Long working-distance water immersion objective lenses are typically used for deep-tissue imaging. However, absorption due to immersion water at 1700 nm is still high and leads to dramatic decrease in signals. In this paper, we demonstrate measurement of absorption spectrum of deuterium oxide (D{sub 2}O) from 1200 nm to 2600 nm, covering the three low water-absorption windows potentially applicable for deep-tissue imaging (1300 nm, 1700 nm, and 2200 nm). We apply this measured result to signal enhancement in MPM at the 1700-nm window. Compared with water immersion, D{sub 2}O immersionmore » enhances signal levels in second-harmonic generation imaging, 3-photon fluorescence imaging, and third-harmonic generation imaging by 8.1, 24.8, and 24.7 times with 1662-nm excitation, in good agreement with theoretical calculation based on our absorption measurement. This suggests D{sub 2}O a promising immersion medium for deep-tissue imaging.« less

A giant enhancement of multiphoton absorption in single-layer molybdenum disulfide

NASA Astrophysics Data System (ADS)

Zhou, Feng; Ji, Wei

Identifying light absorption mechanisms in nanoscale materials, which are more efficient than those observed in bulk semiconductors, are of paramount importance to next-generation, infrared photo-detection. Here, we report considerable enhancement of degenerate two-photon absorption (2PA) and three-photon absorption (3PA) through two-dimensional (2D) excitonic effects in single-layer molybdenum disulfide (1L-MoS2) . We theoretically predict that both degenerate 2PA and 3PA coefficients of 1L-MoS2 are enhanced by 10-1000 times in the near-infrared (NIR), as compared with those of bulk semiconductors. Our theoretical prediction is validated by measuring photocurrents induced by 2PA or 3PA in a 1L-MoS2 photo-detector at room temperature where excitons in the immediate vicinity of the bandgap are transferred to the conduction band by a very small amount of thermal energy and dissociated under an external electric field. Our finding lays theoretical foundation and provides experimental evidence for developing sensitive infrared multiphoton detectors for nano-photonics. This work was supported by National University of Singapore through a research Grant: R144-000-327-112.

Atmospheric Pressure Ionization Permanent Magnet Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

PubMed Central

Vilkov, Andrey N.; Gamage, Chaminda M.; Misharin, Alexander S.; Doroshenko, Vladimir M.; Tolmachev, Dmitry A.; Tarasova, Irina A.; Kharybin, Oleg N.; Novoselov, Konstantin P.; Gorshkov, Michael V.

2007-01-01

A new Fourier Transform Ion Cyclotron Resonance mass spectrometer based on a permanent magnet with an atmospheric pressure ionization source was designed and constructed. A mass resolving power (full-width-at-half-maximum) of up to 80,000 in the electron ionization mode and 25,000 in the electrospray mode was obtained. Also, a mass measurement accuracy at low-ppm level has been demonstrated for peptide mixtures in a mass range of up to 1,200 m/z in the isotopically resolved mass spectra. PMID:17587594

Temperature tuning from direct to inverted bistable electroluminescence in resonant tunneling diodes

NASA Astrophysics Data System (ADS)

Hartmann, F.; Pfenning, A.; Rebello Sousa Dias, M.; Langer, F.; Höfling, S.; Kamp, M.; Worschech, L.; Castelano, L. K.; Marques, G. E.; Lopez-Richard, V.

2017-10-01

We study the electroluminescence (EL) emission of purely n-doped resonant tunneling diodes in a wide temperature range. The paper demonstrates that the EL originates from impact ionization and radiative recombination in the extended collector region of the tunneling device. Bistable current-voltage response and EL are detected and their respective high and low states are tuned under varying temperature. The bistability of the EL intensity can be switched from direct to inverted with respect to the tunneling current and the optical on/off ratio can be enhanced with increasing temperature. One order of magnitude amplification of the optical on/off ratio can be attained compared to the electrical one. Our observation can be explained by an interplay of moderate peak-to-valley current ratios, large resonance voltages, and electron energy loss mechanisms, and thus, could be applied as an alternative route towards optoelectronic applications of tunneling devices.

The role of Upper Hybrid Turbulence on HF Artificial Ionization

NASA Astrophysics Data System (ADS)

Papadopoulos, Konstantinos Dennis; Najmi, Amir; Eliasson, Bengt; Milikh, Gennady

2016-07-01

One of the most fascinating and scientifically interesting phenomena of active space experiments is the discovery of artificial ionization by Todd Pedersen when the HAARP ERP reached the GW level. The phenomenon has been well documented experimentally. A theoretical model based on ionization by energetic electrons accelerated by 50-100 V/m localized electric fields due to Strong Langmuir Turbulence (SLT) near the reflection surface of the HF pump wave, reproduced the observed dynamics of the descending plasma layer quite accurately. A major defect of the model was that the electron temperature in the SLT region was a free parameter. When taken as the 2000 K representing the ambient electron temperature the SLT driven electron flux was insufficient to produce ionization. An equivalent electron temperature of 5000 K or higher was necessary to reproduce the observations. The needed electron heating was attributed to the interaction of the HF at the Upper Hybrid (UH) resonant layer, approximately 5 Km below the reflection region where the HF electric field is perpendicular to the ambient magnetic field. The heated electrons expanded upwards along the magnetic field line and interacted with SLT fields near the resonance region. A consequence of this defect was that the theory could not explain the puzzling double resonance effect. Namely the observation that the ionization level was much stronger when the HF frequency and the UH resonance were a multiple of the electron cyclotron frequency. To remedy this we used a series of Vlasov simulations to explore the HF-plasma interaction in the vicinity of the UH resonance. The simulations followed the evolution of the spectral density of the electric field over a 7.5 MHz frequency band and cm scale lengths and of the electron distribution function over one millisecond for both double resonant and non-resonant cases. Many new features were revealed by the analysis of the simulations such as: 1. Broadening of the wave-number spectral region at the at the UH frequency 2. Excitation of all Bernstein modes associated with cyclotron frequency harmonics both below and above the UH frequency for both the resonant and non0resonant cases. 3. Moderate electron heating, in the form of bulk heating caused by first Bernstein mode, although its wave intensity is more than 20 dB lower than the intensity of the UH branch for all non-resonant cases. 4. Strong generation of non-thermal tails for the resonant cases, by the UH waves downshifted by the lower hybrid frequency when the downshifted frequency was equal to an harmonic of the electron gyro-frequency. The new UH turbulence resolves several f the mysteries associated with artificial ionization and suggests several new observations. Acknowledgment:Work supported by AFOSR MURI grant FA95501410019.

Selective ionization of dissolved organic nitrogen by positive ion atmospheric pressure photoionization coupled with Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Podgorski, David C; McKenna, Amy M; Rodgers, Ryan P; Marshall, Alan G; Cooper, William T

2012-06-05

Dissolved organic nitrogen (DON) comprises a heterogeneous family of organic compounds that includes both well-known biomolecules such as urea or amino acids and more complex, less characterized compounds such as humic and fulvic acids. Typically, DON represents only a small fraction of the total dissolved organic carbon pool and therefore presents inherent problems for chemical analysis and characterization. Here, we demonstrate that DON may be selectively ionized by atmospheric pressure photionization (APPI) and characterized at the molecular level by Fourier transform ion cyclotron resonance mass spectrometry. Unlike electrospray ionization (ESI), APPI ionizes polar and nonpolar compounds, and ionization efficiency is not determined by polarity. APPI is tolerant to salts, due to the thermal treatment inherent to nebulization, and thus avoids salt-adduct formation that can complicate ESI mass spectra. Here, for dissolved organic matter from various aquatic environments, we selectively ionize DON species that are not efficiently ionized by other ionization techniques and demonstrate significant signal-to-noise increase for nitrogen species by use of APPI relative to ESI.

Ionospheric modifications in high frequency heating experiments

NASA Astrophysics Data System (ADS)

Kuo, Spencer P.

2015-01-01

Featured observations in high-frequency (HF) heating experiments conducted at Arecibo, EISCAT, and high frequency active auroral research program are discussed. These phenomena appearing in the F region of the ionosphere include high-frequency heater enhanced plasma lines, airglow enhancement, energetic electron flux, artificial ionization layers, artificial spread-F, ionization enhancement, artificial cusp, wideband absorption, short-scale (meters) density irregularities, and stimulated electromagnetic emissions, which were observed when the O-mode HF heater waves with frequencies below foF2 were applied. The implication and associated physical mechanism of each observation are discussed and explained. It is shown that these phenomena caused by the HF heating are all ascribed directly or indirectly to the excitation of parametric instabilities which instigate anomalous heating. Formulation and analysis of parametric instabilities are presented. The results show that oscillating two stream instability and parametric decay instability can be excited by the O-mode HF heater waves, transmitted from all three heating facilities, in the regions near the HF reflection height and near the upper hybrid resonance layer. The excited Langmuir waves, upper hybrid waves, ion acoustic waves, lower hybrid waves, and field-aligned density irregularities set off subsequent wave-wave and wave-electron interactions, giving rise to the observed phenomena.

Rapid creation of distant entanglement by multiphoton resonant fluorescence

NASA Astrophysics Data System (ADS)

Cohen, Guy Z.; Sham, L. J.

2013-12-01

We study a simple, effective, and robust method for entangling two separate stationary quantum dot spin qubits with high fidelity using multiphoton Gaussian state. The fluorescence signals from the two dots interfere at a beam splitter. The bosonic nature of photons leads, in analogy with the Hong-Ou-Mandel effect, to selective pairing of photon holes (photon absences in the fluorescent signals). As a result, two odd photon number detections at the outgoing beams herald trion entanglement creation, and subsequent reduction of the trions to the spin ground states leads to spin-spin entanglement. The robustness of the Gaussian states is evidenced by the ability to compensate for photon absorption and noise by a moderate increase in the number of photons at the input. We calculate the entanglement generation rate in the ideal, nonideal, and near-ideal detector regimes and find substantial improvement over single-photon schemes in all three regimes. Fast and efficient spin-spin entanglement creation can form the basis for a scalable quantum dot quantum computing network. Our predictions can be tested using current experimental capabilities.

Mapping and controlling ultrafast dynamics of highly excited H 2 molecules by VUV-IR pump-probe schemes

DOE PAGES

Sturm, F. P.; Tong, X. M.; Palacios, A.; ...

2017-01-09

Here, we used ultrashort femtosecond vacuum ultraviolet (VUV) and infrared (IR) pulses in a pump-probe scheme to map the dynamics and nonequilibrium dissociation channels of excited neutral H 2 molecules. A nuclear wave packet is created in the B 1Σmore » $$+\\atop{u}$$ state of the neutral H 2 molecule by absorption of the ninth harmonic of the driving infrared laser field. Due to the large stretching amplitude of the molecule excited in the B 1Σ$$+\\atop{u}$$ electronic state, the effective H 2 + ionization potential changes significantly as the nuclear wave packet vibrates in the bound, highly electronically and vibrationally excited B potential-energy curve. We probed such dynamics by ionizing the excited neutral molecule using time-delayed VUV-or-IR radiation. We identified the nonequilibrium dissociation channels by utilizing three-dimensional momentum imaging of the ion fragments. We also found that different dissociation channels can be controlled, to some extent, by changing the IR laser intensity and by choosing the wavelength of the probe laser light. Furthermore, we concluded that even in a benchmark molecular system such as H 2*, the interpretation of the nonequilibrium multiphoton and multicolor ionization processes is still a challenging task, requiring intricate theoretical analysis.« less

Modeling of ablation threshold dependence on pulse duration for dielectrics with ultrashort pulsed laser

NASA Astrophysics Data System (ADS)

Sun, Mingying; Zhu, Jianqiang; Lin, Zunqi

2017-01-01

We present a numerical model of plasma formation in ultrafast laser ablation on the dielectrics surface. Ablation threshold dependence on pulse duration is predicted with the model and the numerical results for water agrees well with the experimental data for pulse duration from 140 fs to 10 ps. Influences of parameters and approximations of photo- and avalanche-ionization on the ablation threshold prediction are analyzed in detail for various pulse lengths. The calculated ablation threshold is strongly dependent on electron collision time for all the pulse durations. The complete photoionization model is preferred for pulses shorter than 1 ps rather than the multiphoton ionization approximations. The transition time of inverse bremsstrahlung absorption needs to be considered when pulses are shorter than 5 ps and it can also ensure the avalanche ionization (AI) coefficient consistent with that in multiple rate equations (MREs) for pulses shorter than 300 fs. The threshold electron density for AI is only crucial for longer pulses. It is reasonable to ignore the recombination loss for pulses shorter than 100 fs. In addition to thermal transport and hydrodynamics, neglecting the threshold density for AI and recombination could also contribute to the disagreements between the numerical and the experimental results for longer pulses.

Studies of the Twin Helix Parametric-resonance Ionization Cooling Channel with COSY INFINITY

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

J.A. Maloney, K.B. Beard, R.P. Johnson, A. Afanasev, S.A. Bogacz, Y.S. Derbenev, V.S. Morozov, B. Erdelyi

2012-07-01

A primary technical challenge to the design of a high luminosity muon collider is an effective beam cooling system. An epicyclic twin-helix channel utilizing parametric-resonance ionization cooling has been proposed for the final 6D cooling stage. A proposed design of this twin-helix channel is presented that utilizes correlated optics between the horizontal and vertical betatron periods to simultaneously focus transverse motion of the beam in both planes. Parametric resonance is induced in both planes via a system of helical quadrupole harmonics. Ionization cooling is achieved via periodically placed wedges of absorbing material, with intermittent rf cavities restoring longitudinal momentum necessarymore » to maintain stable orbit of the beam. COSY INFINITY is utilized to simulate the theory at first order. The motion of particles around a hyperbolic fixed point is tracked. Comparison is made between the EPIC cooling channel and standard ionization cooling effects. Cooling effects are measured, after including stochastic effects, for both a single particle and a distribution of particles.« less

Ophthalmic imaging using multiphoton microscopy

NASA Astrophysics Data System (ADS)

Teng, Shu-Wen; Peng, Ju-Li; Lin, Huei-Hsing; Wu, Hai-Yin; Lo, Wen; Sun, Yen; Lin, Wei-Chou; Lin, Sung-Jan; Jee, Shiou-Hwa; Tan, Hsin-Yuan; Dong, Chen-Yuan

2005-04-01

This purpose of this study is to demonstrate the feasibility of using multiphoton microscopy in ophthalmologic imaging. Without the introduction of extrinsic fluorescence molecules, multiphoton induced autofluorescence and second harmonic generation signals can be used to obtain useful structural information of normal and diseased corneas. Our work can potentially lead to the in vivo application of multiphoton microscopy in investigating corneal physiology and pathologies.

Multiphoton gradient index endoscopy for evaluation of diseased human prostatic tissue ex vivo

NASA Astrophysics Data System (ADS)

Huland, David M.; Jain, Manu; Ouzounov, Dimitre G.; Robinson, Brian D.; Harya, Diana S.; Shevchuk, Maria M.; Singhal, Paras; Xu, Chris; Tewari, Ashutosh K.

2014-11-01

Multiphoton microscopy can instantly visualize cellular details in unstained tissues. Multiphoton probes with clinical potential have been developed. This study evaluates the suitability of multiphoton gradient index (GRIN) endoscopy as a diagnostic tool for prostatic tissue. A portable and compact multiphoton endoscope based on a 1-mm diameter, 8-cm length GRIN lens system probe was used. Fresh ex vivo samples were obtained from 14 radical prostatectomy patients and benign and malignant areas were imaged and correlated with subsequent H&E sections. Multiphoton GRIN endoscopy images of unfixed and unprocessed prostate tissue at a subcellular resolution are presented. We note several differences and identifying features of benign versus low-grade versus high-grade tumors and are able to identify periprostatic tissues such as adipocytes, periprostatic nerves, and blood vessels. Multiphoton GRIN endoscopy can be used to identify both benign and malignant lesions in ex vivo human prostate tissue and may be a valuable diagnostic tool for real-time visualization of suspicious areas of the prostate.

Optimizing the ionization and energy absorption of laser-irradiated clusters

NASA Astrophysics Data System (ADS)

Kundu, M.; Bauer, D.

2008-03-01

It is known that rare-gas or metal clusters absorb incident laser energy very efficiently. However, due to the intricate dependencies on all the laser and cluster parameters, it is difficult to predict under which circumstances ionization and energy absorption are optimal. With the help of three-dimensional particle-in-cell simulations of xenon clusters (up to 17256 atoms), it is shown that for a given laser pulse energy and cluster, an optimum wavelength exists that corresponds to the approximate wavelength of the transient, linear Mie-resonance of the ionizing cluster at an early stage of negligible expansion. In a single ultrashort laser pulse, the linear resonance at this optimum wavelength yields much higher absorption efficiency than in the conventional, dual-pulse pump-probe setup of linear resonance during cluster expansion.

Resonance-enhanced two-photon ionization spectroscopy and theoretical calculations of 3,5-difluoroanisole and its Ar-containing complex.

PubMed

Zhang, Lijuan; Dong, Changwu; Cheng, Min; Hu, Lili; Du, Yikui; Zhu, Qihe; Zhang, Cunhao

2012-10-01

The structure and vibrations of 3,5-difluoroanisole (3,5-DFA) in the first electronically excited (S(1)) state were studied by mass-analyzed resonant two-photon ionization (R2PI) technique as well as the quantum chemical calculations. The ab initio and density functional theory (DFT) calculations reveal that only one structure is stable for each of the S(0), S(1), and D(0) states. In the one color R2PI spectrum, the band origin of the S(1)←S(0) electronic transition (0(0) band) of 3,5-DFA is found to be 37,595±3 cm(-1). In the S(1) state, most of the bands observed are related to the in-plane ring deformation and out-of-plane bending vibrations. The adiabatic ionization energy (IE) of 3,5-DFA is determined to be 70,096±15 cm(-1) by the two color R2PI technique, in agreement with the values predicted by the DFT approaches. The dihalogen-substitution effects on the molecular structure, vibrational frequencies, and electronic transition and ionization energies were discussed in detail. The van der Waals complex of 3,5-DFA with argon (3,5-DFA···Ar) was also observed and studied. The 0(0) band of 3,5-DFA···Ar complex is red-shifted by about 9 cm(-1) with respect to that of 3,5-DFA. Both the experimental data and the calculated results indicate that the formation of 3,5-DFA···Ar complex gives only a weak influence on the properties of 3,5-DFA moiety. Copyright © 2012 Elsevier B.V. All rights reserved.

On-chip photonic transistor based on the spike synchronization in circuit QED

NASA Astrophysics Data System (ADS)

Gül, Yusuf

2018-03-01

We consider the single photon transistor in coupled cavity system of resonators interacting with multilevel superconducting artificial atom simultaneously. Effective single mode transformation is used for the diagonalization of the Hamiltonian and impedance matching in terms of the normal modes. Storage and transmission of the incident field are described by the interactions between the cavities controlling the atomic transitions of lowest lying states. Rabi splitting of vacuum-induced multiphoton transitions is considered in input/output relations by the quadrature operators in the absence of the input field. Second-order coherence functions are employed to investigate the photon blockade and delocalization-localization transitions of cavity fields. Spontaneous virtual photon conversion into real photons is investigated in localized and oscillating regimes. Reflection and transmission of cavity output fields are investigated in the presence of the multilevel transitions. Accumulation and firing of the reflected and transmitted fields are used to investigate the synchronization of the bunching spike train of transmitted field and population imbalance of cavity fields. In the presence of single photon gate field, gain enhancement is explained for transmitted regime.

Application of parametric equations of motion to study the resonance coalescence in H2(+).

PubMed

Kalita, Dhruba J; Gupta, Ashish K

2012-12-07

Recently, occurrence of coalescence point was reported in H(2)(+) undergoing multiphoton dissociation in strong laser field. We have applied parametric equations of motion and smooth exterior scaling method to study the coalescence phenomenon of H(2)(+). The advantage of this method is that one can easily trace the different states that are changing as the field parameters change. It was reported earlier that in the parameter space, only two bound states coalesce [R. Lefebvre, O. Atabek, M. Sindelka, and N. Moiseyev, Phys. Rev. Lett. 103, 123003 (2009)]. However, it is found that increasing the accuracy of the calculation leads to the coalescence between resonance states originating from the bound and the continuum states. We have also reported many other coalescence points.

All-optical switch and transistor gated by one stored photon.

PubMed

Chen, Wenlan; Beck, Kristin M; Bücker, Robert; Gullans, Michael; Lukin, Mikhail D; Tanji-Suzuki, Haruka; Vuletić, Vladan

2013-08-16

The realization of an all-optical transistor, in which one "gate" photon controls a "source" light beam, is a long-standing goal in optics. By stopping a light pulse in an atomic ensemble contained inside an optical resonator, we realized a device in which one stored gate photon controls the resonator transmission of subsequently applied source photons. A weak gate pulse induces bimodal transmission distribution, corresponding to zero and one gate photons. One stored gate photon produces fivefold source attenuation and can be retrieved from the atomic ensemble after switching more than one source photon. Without retrieval, one stored gate photon can switch several hundred source photons. With improved storage and retrieval efficiency, our work may enable various new applications, including photonic quantum gates and deterministic multiphoton entanglement.

Novel two-step laser ablation and ionization mass spectrometry (2S-LAIMS) of actor-spectator ice layers: Probing chemical composition of D{sub 2}O ice beneath a H{sub 2}O ice layer

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

Yang, Rui, E-mail: ryang73@ustc.edu; Gudipati, Murthy S., E-mail: gudipati@jpl.nasa.gov

2014-03-14

In this work, we report for the first time successful analysis of organic aromatic analytes imbedded in D{sub 2}O ices by novel infrared (IR) laser ablation of a layered non-absorbing D{sub 2}O ice (spectator) containing the analytes and an ablation-active IR-absorbing H{sub 2}O ice layer (actor) without the analyte. With these studies we have opened up a new method for the in situ analysis of solids containing analytes when covered with an IR laser-absorbing layer that can be resonantly ablated. This soft ejection method takes advantage of the tenability of two-step infrared laser ablation and ultraviolet laser ionization mass spectrometry,more » previously demonstrated in this lab to study chemical reactions of polycyclic aromatic hydrocarbons (PAHs) in cryogenic ices. The IR laser pulse tuned to resonantly excite only the upper H{sub 2}O ice layer (actor) generates a shockwave upon impact. This shockwave penetrates the lower analyte-containing D{sub 2}O ice layer (spectator, a non-absorbing ice that cannot be ablated directly with the wavelength of the IR laser employed) and is reflected back, ejecting the contents of the D{sub 2}O layer into the vacuum where they are intersected by a UV laser for ionization and detection by a time-of-flight mass spectrometer. Thus, energy is transmitted from the laser-absorbing actor layer into the non-absorbing spectator layer resulting its ablation. We found that isotope cross-contamination between layers was negligible. We also did not see any evidence for thermal or collisional chemistry of PAH molecules with H{sub 2}O molecules in the shockwave. We call this “shockwave mediated surface resonance enhanced subsurface ablation” technique as “two-step laser ablation and ionization mass spectrometry of actor-spectator ice layers.” This method has its roots in the well-established MALDI (matrix assisted laser desorption and ionization) method. Our method offers more flexibility to optimize both the processes—ablation and ionization. This new technique can thus be potentially employed to undertake in situ analysis of materials imbedded in diverse media, such as cryogenic ices, biological samples, tissues, minerals, etc., by covered with an IR-absorbing laser ablation medium and study the chemical composition and reaction pathways of the analyte in its natural surroundings.« less

Observation of new even-parity states of Sm I by resonance ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Jayasekharan, T.; Razvi, M. A. N.; Bhale, G. L.

1996-04-01

Resonance ionization mass spectrometry is applied to investigate high-lying even-parity states of Sm I. Eighty-six even-parity states of Sm I are discovered in the region 32950-36000 cm -1 . Absolute energies of these states are measured with an uncertainty of +/- 0.3 cm -1 , and total angular momenta are uniquely assigned for most of them.

Low-energy electron elastic scattering and impact ionization with hydrogenlike helium in Debye plasmas

NASA Astrophysics Data System (ADS)

Li, Jun; Zhang, Song Bin; Ye, Bang Jiao; Wang, Jian Guo; Janev, R. K.

2017-09-01

Low-energy electron elastic scattering and impact ionization with hydrogenlike helium in Debye plasmas have been investigated by employing the exterior complex scaling method. The interactions between charged particles in the plasmas have been represented by Debye-Hückel potentials. The 1 s -1 s elastic collision strengths below the n =2 excitation threshold of He+ dominated by resonance structures are calculated for different screening lengths. As the screening strength increases, the resonance peaks studied [2(1,0) 2 +1Se,3Po,1De , and 2(0,1) 2 +1Po] exhibit blueshifts and then redshifts with a further increase of the screening strength, which results in dramatic changes of the collision strengths. It is found that these dynamic variation features of the resonances are related to the changes of energy levels of He+ in the screened potential and geometric configurations of resonances. Triple-differential-ionization cross sections in coplanar geometries at 6-Ry incident electron energy are also reported, significant changes are observed with varying screening length.

In vivo multiphoton tomography and fluorescence lifetime imaging of human brain tumor tissue.

PubMed

Kantelhardt, Sven R; Kalasauskas, Darius; König, Karsten; Kim, Ella; Weinigel, Martin; Uchugonova, Aisada; Giese, Alf

2016-05-01

High resolution multiphoton tomography and fluorescence lifetime imaging differentiates glioma from adjacent brain in native tissue samples ex vivo. Presently, multiphoton tomography is applied in clinical dermatology and experimentally. We here present the first application of multiphoton and fluorescence lifetime imaging for in vivo imaging on humans during a neurosurgical procedure. We used a MPTflex™ Multiphoton Laser Tomograph (JenLab, Germany). We examined cultured glioma cells in an orthotopic mouse tumor model and native human tissue samples. Finally the multiphoton tomograph was applied to provide optical biopsies during resection of a clinical case of glioblastoma. All tissues imaged by multiphoton tomography were sampled and processed for conventional histopathology. The multiphoton tomograph allowed fluorescence intensity- and fluorescence lifetime imaging with submicron spatial resolution and 200 picosecond temporal resolution. Morphological fluorescence intensity imaging and fluorescence lifetime imaging of tumor-bearing mouse brains and native human tissue samples clearly differentiated tumor and adjacent brain tissue. Intraoperative imaging was found to be technically feasible. Intraoperative image quality was comparable to ex vivo examinations. To our knowledge we here present the first intraoperative application of high resolution multiphoton tomography and fluorescence lifetime imaging of human brain tumors in situ. It allowed in vivo identification and determination of cell density of tumor tissue on a cellular and subcellular level within seconds. The technology shows the potential of rapid intraoperative identification of native glioma tissue without need for tissue processing or staining.

Resonant two-photon ionization and mass-analyzed threshold ionization spectroscopy of p-vinylaniline

NASA Astrophysics Data System (ADS)

Tzeng, Sheng Yuan; Dong, Changwu; Tzeng, Wen Bih

2012-10-01

We report the vibronic and cation spectra of p-vinylaniline, which are recorded by using the resonant two-photon ionization and the mass-analyzed threshold ionization spectroscopic techniques. The band origin of the S1 ← S0 electronic transition appears at 31,490 ± 2 cm-1 and the adiabatic ionization energy is determined to be 59,203 ± 5 cm-1. Due to the nature of the substituent, the amino and vinyl groups lead to lower electronic excitation and ionization energies by a few thousand wave numbers. Most of the observed active modes result from the in-plane ring deformation and substituent-sensitive vibrations of this molecule in the electronically excited S1 and cationic ground D0 states. By comparing the frequencies of the observed active vibrations, one may conclude that the molecular geometry and the vibrational coordinates of these modes of the p-vinylaniline cation in the D0 state resemble those of the neutral species in the S1 state.

Enhanced eumelanin emission by stepwise three-photon excitation

NASA Astrophysics Data System (ADS)

Kerimo, Josef; Rajadhyaksha, Milind; DiMarzio, Charles A.

2011-03-01

Eumelanin fluorescence from Sepia officinalis and black human hair was activated with near-infrared radiation and multiphoton excitation. A third order multiphoton absorption by a step-wise process appears to be the underlying mechanism. The activation was caused by a photochemical process since it could not be reproduced by simple heating. Both fluorescence and brightfield imaging indicate the near-infrared irradiation caused photodamage to the eumelanin and the activated emission originated from the photodamaged region. At least two different components with about thousand-fold enhanced fluorescence were activated and could be distinguished by their excitation properties. One component was excited with wavelengths in the visible region and exhibited linear absorption dependence. The second component could be excited with near-infrared wavelengths and had a third order dependence on the laser power. The third order dependence is explained by a step-wise excited state absorption (ESA) process since it could be observed equally with the CW and femtosecond lasers. The new method for photoactivating the eumelanin fluorescence was used to map the melanin content in human hair.

First results on Ge resonant laser photoionization in hollow cathode lamp

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

Scarpa, Daniele, E-mail: daniele.scarpa@lnl.infn.it; Andrighetto, Alberto; Barzakh, Anatoly

2016-02-15

In the framework of the research and development activities of the SPES project regarding the optimization of the radioactive beam production, a dedicated experimental study has been recently started in order to investigate the possibility of in-source ionization of germanium using a set of tunable dye lasers. Germanium is one of the beams to be accelerated by the SPES ISOL facility, which is under construction at Legnaro INFN Laboratories. The three-step, two color ionization schemes have been tested using a Ge hollow cathode lamp. The slow and the fast optogalvanic signals were detected and averaged by an oscilloscope as amore » proof of the laser ionization inside the lamp. As a result, several wavelength scans across the resonances of ionization schemes were collected with the fast optogalvanic signal. Some comparisons of ionization efficiency for different ionization schemes were made. Furthermore, saturation curves of the first excitation transitions have been obtained. This investigation method and the setup built in the laser laboratory of the SPES project can be applied for the photo-ionization scheme studies also for the other possible radioactive elements.« less

Development and characterization of non-resonant multiphoton photoacoustic spectroscopy (NMPPAS) for brain tumor margining

NASA Astrophysics Data System (ADS)

Dahal, Sudhir

During tumor removal surgery, due to the problems associated with obtaining high-resolution, real-time chemical images of where exactly the tumor ends and healthy tissue begins (tumor margining), it is often necessary to remove a much larger volume of tissue than the tumor itself. In the case of brain tumor surgery, however, it is extremely unsafe to remove excess tissue. Therefore, without an accurate image of the tumor margins, some of the tumor's finger-like projections are inevitably left behind in the surrounding parenchyma to grow again. For this reason, the development of techniques capable of providing high-resolution real-time images of tumor margins up to centimeters below the surface of a tissue is ideal for the diagnosis and treatment of tumors, as well as surgical guidance during brain tumor excision. A novel spectroscopic technique, non-resonant multiphoton photoacoustic spectroscopy (NMPPAS), is being developed with the capabilities of obtaining high-resolution subsurface chemical-based images of underlying tumors. This novel technique combines the strengths of multiphoton tissue spectroscopy and photoacoustic spectroscopy into a diagnostic methodology that will, ultimately, provide unparalleled chemical information and images to provide the state of sub-surface tissues. The NMPPAS technique employs near-infrared light (in the diagnostic window) to excite ultraviolet and/or visible light absorbing species deep below the tissue's surface. Once a multiphoton absorption event occurs, non-radiative relaxation processes generates a localized thermal expansion and subsequent acoustic wave that can be detected using a piezoelectric transducer. Since NMPPAS employs an acoustic detection modality, much deeper diagnoses can be performed than that is possible using current state of the art high-resolution chemical imaging techniques such as multiphoton fluorescence spectroscopy. NMPPAS was employed to differentiate between excised brain tumors (astrocytoma III) and healthy tissue with over 99% accuracy. NMPPAS spectral features showed evident differences between tumor and healthy tissues, and ratiometric analysis ensured that only a few wavelengths could be used for excitation instead of using numerous wavelength excitations to create spectra. This process would significantly reduce the analysis time while maintaining the same degree of accuracy. Tissue phantoms were fabricated in order to characterize the properties of NMPPAS. Scattering particles were doped into the phantoms to simulate their light scattering properties to real tissues. This allowed for better control over shape, size, reproducibility and doping in the sample while maintaining the light-tissue interaction properties of real tissue. To make NMPPAS viable for clinical applications, the technique was characterized to determine the spatial (lateral and longitudinal) resolution, depth of penetration and its ability to image in three-dimension through layers of tissue. Both resolutions were determined to be near-cellular level resolution (50-70 microm), obtained initially with the aid of the technique of multiphoton fluorescence, and later verified using NMPPAS imaging. Additionally, the maximum depth of penetration and detection was determined to be about 1.4cm, making the technique extremely suitable to margin tumors from underlying tissues in the brain. The capability of NMPPAS to detect and image layers that lie beneath other structures and blood vessels was also investigated. Three-dimensional images were obtained for the first time using NMPPAS. The images were obtained from different depths and structures were imaged through other layers of existing structures in the sample. This verified that NMPPAS was capable of detecting and imaging structures that lie embedded within the tissues. NMPPAS images of embedded structures were also obtained with the presence of hemoglobin, which is potentially the largest source of background in blood-perfused tissues, thus showing that the technique is capable of detecting and differentiating in blood-perfused samples.

Three-dimensional femtosecond laser processing for lab-on-a-chip applications

NASA Astrophysics Data System (ADS)

Sima, Felix; Sugioka, Koji; Vázquez, Rebeca Martínez; Osellame, Roberto; Kelemen, Lóránd; Ormos, Pal

2018-02-01

The extremely high peak intensity associated with ultrashort pulse width of femtosecond laser allows us to induce nonlinear interaction such as multiphoton absorption and tunneling ionization with materials that are transparent to the laser wavelength. More importantly, focusing the femtosecond laser beam inside the transparent materials confines the nonlinear interaction only within the focal volume, enabling three-dimensional (3D) micro- and nanofabrication. This 3D capability offers three different schemes, which involve undeformative, subtractive, and additive processing. The undeformative processing preforms internal refractive index modification to construct optical microcomponents including optical waveguides. Subtractive processing can realize the direct fabrication of 3D microfluidics, micromechanics, microelectronics, and photonic microcomponents in glass. Additive processing represented by two-photon polymerization enables the fabrication of 3D polymer micro- and nanostructures for photonic and microfluidic devices. These different schemes can be integrated to realize more functional microdevices including lab-on-a-chip devices, which are miniaturized laboratories that can perform reaction, detection, analysis, separation, and synthesis of biochemical materials with high efficiency, high speed, high sensitivity, low reagent consumption, and low waste production. This review paper describes the principles and applications of femtosecond laser 3D micro- and nanofabrication for lab-on-a-chip applications. A hybrid technique that promises to enhance functionality of lab-on-a-chip devices is also introduced.

Electron Capture Dissociation of Divalent Metal-adducted Sulfated N-Glycans Released from Bovine Thyroid Stimulating Hormone

NASA Astrophysics Data System (ADS)

Zhou, Wen; Håkansson, Kristina

2013-11-01

Sulfated N-glycans released from bovine thyroid stimulating hormone (bTSH) were ionized with the divalent metal cations Ca2+, Mg2+, and Co by electrospray ionization (ESI). These metal-adducted species were subjected to infrared multiphoton dissociation (IRMPD) and electron capture dissociation (ECD) and the corresponding fragmentation patterns were compared. IRMPD generated extensive glycosidic and cross-ring cleavages, but most product ions suffered from sulfonate loss. Internal fragments were also observed, which complicated the spectra. ECD provided complementary structural information compared with IRMPD, and all observed product ions retained the sulfonate group, allowing sulfonate localization. To our knowledge, this work represents the first application of ECD towards metal-adducted sulfated N-glycans released from a glycoprotein. Due to the ability of IRMPD and ECD to provide complementary structural information, the combination of the two strategies is a promising and valuable tool for glycan structural characterization. The influence of different metal ions was also examined. Calcium adducts appeared to be the most promising species because of high sensitivity and ability to provide extensive structural information.

Investigation of depilatory mechanism by use of multiphoton fluorescent microscopy

NASA Astrophysics Data System (ADS)

Lin, Chiao-Ying; Lee, Gie-ne; Jee, Shiou-Hwa; Dong, Chen-Yuan; Lin, Sung-Jan

2007-07-01

Transdermal drug delivery provides a non-invasive route of drug administration, and can be a alternative method to oral delivery and injection. The stratum corneum (SC) of skin acts as the main barrier to transdermal drug delivery. Studies suggest that depilatory enhances permeability of drug through the epidermis. However, transdermal delivery pathway and mechanism are not completely understood. Previous studies have found that depilatory changes the keratinocytes of epidermis, and cause the protein in combination with lipid extraction of SC to become disordered. Nevertheless, those studies did not provide images of those processes. The aim of this study is to characterize the penetration enhancing effect of depilatory agent and the associated structural alterations of stratum corneum. Fresh human foreskin is treated by a depilatory agent for 10 minutes and then subjected to the treatment of fluorescent model drugs of hydrophilic rhodamine and hydrophobic rhodamine-RE. The penetration of model drugs is imaged and quantified by multiphoton microscopy. Our results showed that the penetration of both hydrophilic and hydrophobic agents can be enhanced and multifocal detachment of surface corneocytes is revealed. Nile red staining revealed, instead of a regular motar distribution of lipid around the brick of corneocytes, a disorganized and homogenized pattern of lipid distribution. We concluded that depilatory agents enhance drug penetration by disrupting both the cellular integrity of corneocytes and the regular packing of intercellular lipid of stratum corneum.

Infrared laser induced population transfer and parity selection in 14NH3: A proof of principle experiment towards detecting parity violation in chiral molecules

NASA Astrophysics Data System (ADS)

Dietiker, P.; Miloglyadov, E.; Quack, M.; Schneider, A.; Seyfang, G.

2015-12-01

We have set up an experiment for the efficient population transfer by a sequential two photon—absorption and stimulated emission—process in a molecular beam to prepare quantum states of well defined parity and their subsequent sensitive detection. This provides a proof of principle for an experiment which would allow for parity selection and measurement of the time evolution of parity in chiral molecules, resulting in a measurement of the parity violating energy difference ΔpvE between enantiomers of chiral molecules. Here, we present first results on a simple achiral molecule demonstrating efficient population transfer (about 80% on the average for each step) and unperturbed persistence of a selected excited parity level over flight times of about 1.3 ms in the beam. In agreement with model calculations with and without including nuclear hyperfine structure, efficient population transfer can be achieved by a rather simple implementation of the rapid adiabatic passage method of Reuss and coworkers and considering also the stimulated Raman adiabatic passage technique of Bergmann and coworkers as an alternative. The preparation step uses two powerful single mode continuous wave optical parametric oscillators of high frequency stability and accuracy. The detection uses a sensitive resonantly enhanced multiphoton ionization method after free flight lengths of up to 0.8 m in the molecular beam. Using this technique, we were able to also resolve the nuclear hyperfine structure in the rovibrational levels of the ν1 and ν3 fundamentals as well as the 2ν4 overtone of 14NH3, for which no previous data with hyperfine resolution were available. We present our new results on the quadrupole coupling constants for the ν1, ν3, and 2ν4 levels in the context of previously known data for ν2 and its overtone, as well as ν4, and the ground state. Thus, now, 14N quadrupole coupling constants for all fundamentals and some overtones of 14NH3 are known and can be used for further theoretical analysis.

Infrared laser induced population transfer and parity selection in (14)NH3: A proof of principle experiment towards detecting parity violation in chiral molecules.

PubMed

Dietiker, P; Miloglyadov, E; Quack, M; Schneider, A; Seyfang, G

2015-12-28

We have set up an experiment for the efficient population transfer by a sequential two photon-absorption and stimulated emission-process in a molecular beam to prepare quantum states of well defined parity and their subsequent sensitive detection. This provides a proof of principle for an experiment which would allow for parity selection and measurement of the time evolution of parity in chiral molecules, resulting in a measurement of the parity violating energy difference ΔpvE between enantiomers of chiral molecules. Here, we present first results on a simple achiral molecule demonstrating efficient population transfer (about 80% on the average for each step) and unperturbed persistence of a selected excited parity level over flight times of about 1.3 ms in the beam. In agreement with model calculations with and without including nuclear hyperfine structure, efficient population transfer can be achieved by a rather simple implementation of the rapid adiabatic passage method of Reuss and coworkers and considering also the stimulated Raman adiabatic passage technique of Bergmann and coworkers as an alternative. The preparation step uses two powerful single mode continuous wave optical parametric oscillators of high frequency stability and accuracy. The detection uses a sensitive resonantly enhanced multiphoton ionization method after free flight lengths of up to 0.8 m in the molecular beam. Using this technique, we were able to also resolve the nuclear hyperfine structure in the rovibrational levels of the ν1 and ν3 fundamentals as well as the 2ν4 overtone of (14)NH3, for which no previous data with hyperfine resolution were available. We present our new results on the quadrupole coupling constants for the ν1, ν3, and 2ν4 levels in the context of previously known data for ν2 and its overtone, as well as ν4, and the ground state. Thus, now, (14)N quadrupole coupling constants for all fundamentals and some overtones of (14)NH3 are known and can be used for further theoretical analysis.

FAR-INFRARED SPECTROSCOPY OF CATIONIC POLYCYCLIC AROMATIC HYDROCARBONS: ZERO KINETIC ENERGY PHOTOELECTRON SPECTROSCOPY OF PENTACENE VAPORIZED FROM LASER DESORPTION

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

Zhang Jie; Han Fangyuan; Pei Linsen

2010-05-20

The distinctive set of infrared (IR) emission bands at 3.3, 6.2, 7.7, 8.6, and 11.3 {mu}m are ubiquitously seen in a wide variety of astrophysical environments. They are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. However, not a single PAH species has yet been identified in space, as the mid-IR vibrational bands are mostly representative of functional groups and thus do not allow one to fingerprint individual PAH molecules. In contrast, the far-IR (FIR) bands are sensitive to the skeletal characteristics of a molecule, hence they are important for chemical identification of unknown species. With an aim to offermore » laboratory astrophysical data for the Herschel Space Observatory, Stratospheric Observatory for Infrared Astronomy, and similar future space missions, in this work we report neutral and cation FIR spectroscopy of pentacene (C{sub 22}H{sub 14}), a five-ring PAH molecule. We report three IR active modes of cationic pentacene at 53.3, 84.8, and 266 {mu}m that may be detectable by space missions such as the SAFARI instrument on board SPICA. In the experiment, pentacene is vaporized from a laser desorption source and cooled by a supersonic argon beam. We have obtained results from two-color resonantly enhanced multiphoton ionization and two-color zero kinetic energy photoelectron (ZEKE) spectroscopy. Several skeletal vibrational modes of the first electronically excited state of the neutral species and those of the cation are assigned, with the aid of ab initio and density functional calculations. Although ZEKE is governed by the Franck-Condon principle different from direct IR absorption or emission, vibronic coupling in the long ribbon-like molecule results in the observation of a few IR active modes. Within the experimental resolution of {approx}7 cm{sup -1}, the frequency values from our calculation agree with the experiment for the cation, but differ for the electronically excited intermediate state. Consequently, modeling of the intensity distribution is difficult and may require explicit inclusion of vibronic interactions.« less

Spectroscopy of LiCa and RbSr Molecules on Helium Nanodroplets

NASA Astrophysics Data System (ADS)

Lackner, Florian; Krois, Gunter; Ernst, Wolfgang E.

2013-06-01

We report on the investigation of mixed alkali metal (Ak) - alkaline earth metal (Ake) molecules on the surface of helium nanodroplets (He_{N}). These molecules have recently attracted considerable attention as candidates for the formation of ultracold molecules with a magnetic and an electronic dipole moment. In our experiments, LiCa and RbSr molecules are formed in a sequential pick-up process in their X^{2}Σ^{+} ground state and cool down rapidly to the droplet temperature of 0.38 K. Excitation spectra of LiCa and RbSr were recorded by using resonance enhanced multi-photon ionization time-of-flight (REMPI-TOF) spectroscopy and laser induced fluorescence (LIF) spectroscopy. On the helium droplet, vibronic transitions in Ak-Ake molecules are broadened and show a characteristic asymmetric peak form, which is caused by the interaction between the molecule and the superfluid He_{N} environment. For the lower electronic transitions in LiCa and RbSr progressions of vibrational bands excited from the X^{2}Σ^{+} (ν'' = 0) state are observed. The LiCa spectra can be compared to molecular beam experiments, which enables the assignment of three band systems near 15260 cm^{-1}, 19300 cm^{-1} and 22120 cm^{-1} as ^{2}Σ^{+}, ^{2}Π_{Ω} and ^{2}Π band, respectively. In the RbSr excitation spectrum we observe a vibrationally resolved band system near 14020 cm^{-1}. Upon electronic excitation, a fraction of the molecules desorb from the droplet surface and dispersed fluorescence spectra allow to study the X^{2}Σ^{+} ground state and excited states of free Ak-Ake molecules. H. Hara, Y. Takasu, Y. Yamaoka, J.M. Doyle, Y. Takahashi, Phys. Rev. Lett. 106, 205304 (2011) C. Callegari and W. E. Ernst, Helium Droplets as Nanocryostats for Molecular Spectroscopy - from the Vacuum Ultraviolet to the Microwave Regime, in: Handbook of High-Resolution Spectroscopy, eds. M. Quack and F. Merkt, John Wiley & Sons, Chichester, (2011) L. M. Russon, G. K. Rothschopf, M. D. Morse, A. I. Boldyrev, J. Simons, J. Chem. Phys. 109, 6655-6665 (1998)

Thermal Decomposition Mechanisms of Lignin Model Compounds: From Phenol to Vanillin

NASA Astrophysics Data System (ADS)

Scheer, Adam Michael

Lignin is a complex, aromatic polymer abundant in cellulosic biomass (trees, switchgrass etc.). Thermochemical breakdown of lignin for liquid fuel production results in undesirable polycyclic aromatic hydrocarbons that lead to tar and soot byproducts. The fundamental chemistry governing these processes is not well understood. We have studied the unimolecular thermal decomposition mechanisms of aromatic lignin model compounds using a miniature SiC tubular reactor. Products are detected and characterized using time-of-flight mass spectrometry with both single photon (118.2 nm; 10.487 eV) and 1 + 1 resonance-enhanced multiphoton ionization (REMPI) as well as matrix isolation infrared spectroscopy. Gas exiting the heated reactor (300 K--1600 K) is subject to a free expansion after a residence time of approximately 100 micros. The expansion into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. By understanding the unimolecular fragmentation patterns of phenol (C6H5OH), anisole (C6H 5OCH3) and benzaldehyde (C6H5CHO), the more complicated thermocracking processes of the catechols (HO-C 6H4-OH), methoxyphenols (HO-C6H4-OCH 3) and hydroxybenzaldehydes (HO-C6H4-CHO) can be interpreted. These studies have resulted in a predictive model that allows the interpretation of vanillin, a complex phenolic ether containing methoxy, hydroxy and aldehyde functional groups. This model will serve as a guide for the pyrolyses of larger systems including lignin monomers such as coniferyl alcohol. The pyrolysis mechanisms of the dimethoxybenzenes (H3C-C 6H4-OCH3) and syringol, a hydroxydimethoxybenzene have also been studied. These results will aid in the understanding of the thermal fragmentation of sinapyl alcohol, the most complex lignin monomer. In addition to the model compound work, pyrolyisis of biomass has been studied via the pulsed laser ablation of poplar wood. With the REMPI scheme, aromatic lignin decomposition products are directly and selectively detected. A number of these products are the lignin model compounds listed above, providing a direct link between the model compound studies and the pyrolysis of actual biomass.

Characterization of non-polar aromatic hydrocarbons in crude oil using atmospheric pressure laser ionization and Fourier transform ion cyclotron resonance mass spectrometry (APLI FT-ICR MS).

PubMed

Schrader, Wolfgang; Panda, Saroj K; Brockmann, Klaus J; Benter, Thorsten

2008-07-01

We report on the successful application of the recently introduced atmospheric pressure laser ionization (APLI) method as a novel tool for the analysis of crude oil and its components. Using Fourier transform ion cyclotron resonance mass spectrometry, unambiguous determination of key compounds in this complex matrix with unprecedented sensitivity is presented.

Photon-momentum transfer in molecular photoionization

NASA Astrophysics Data System (ADS)

Chelkowski, Szczepan; Bandrauk, André D.

2018-05-01

In most models and theoretical calculations describing multiphoton ionization by infrared light, the dipole approximation is used. This is equivalent to setting the very small photon momentum to zero. Using numerical solutions of the (nondipole) three-dimensional time-dependent Schrödinger equation for one electron in a H2+ molecular ion we investigate the effect the photon-momentum transfer to the photoelectron in an H2+ ion in various regimes. We find that the photon-momentum transfer in a molecule is very different from the transfer in atoms due to two-center interference effects. The photon-momentum transfer is very sensitive to the symmetry of the initial electronic state and is strongly dependent on the internuclear distance and on the ellipticity of the laser.

An ultracold potassium Rydberg source for experiments in quantum optics and many-body physics

NASA Astrophysics Data System (ADS)

Conover, Charles; Dupre, Pamela; Tong, Ai Phuong; Sanon, Carlvin; Clarke, Kevin; Doolittle, Brian; Louria, Stephen; Adamson, Philip

2017-04-01

We report on the development of an apparatus for the study of quantum dynamics of Rydberg atoms of potassium. Samples of Rydberg atoms at 1 mK and varying density are excited in a magneto-optical trap of 107 K-39 atoms. The atoms are excited to Rydberg states in a steps from 4s to 5p and from 5p to ns and nd states using stabilized external-cavity diode lasers at 405 nm and 980 nm. Selective field ionization and detection with microchannel plates provides a platform for spectroscopic measurements in potassium, exploration of multiphoton processes, and experiments on cold atom collisions. This research was supported by the National Science Foundation under Grant PHY-1126599.

Pediatric providers and radiology examinations: knowledge and comfort levels regarding ionizing radiation and potential complications of imaging.

PubMed

Wildman-Tobriner, Benjamin; Parente, Victoria M; Maxfield, Charles M

2017-12-01

Pediatric providers should understand the basic risks of the diagnostic imaging tests they order and comfortably discuss those risks with parents. Appreciating providers' level of understanding is important to guide discussions and enhance relationships between radiologists and pediatric referrers. To assess pediatric provider knowledge of diagnostic imaging modalities that use ionizing radiation and to understand provider concerns about risks of imaging. A 6-question survey was sent via email to 390 pediatric providers (faculty, trainees and midlevel providers) from a single academic institution. A knowledge-based question asked providers to identify which radiology modalities use ionizing radiation. Subjective questions asked providers about discussions with parents, consultations with radiologists, and complications of imaging studies. One hundred sixty-nine pediatric providers (43.3% response rate) completed the survey. Greater than 90% of responding providers correctly identified computed tomography (CT), fluoroscopy and radiography as modalities that use ionizing radiation, and ultrasound and magnetic resonance imaging (MRI) as modalities that do not. Fewer (66.9% correct, P<0.001) knew that nuclear medicine utilizes ionizing radiation. A majority of providers (82.2%) believed that discussions with radiologists regarding ionizing radiation were helpful, but 39.6% said they rarely had time to do so. Providers were more concerned with complications of sedation and cost than they were with radiation-induced cancer, renal failure or anaphylaxis. Providers at our academic referral center have a high level of basic knowledge regarding modalities that use ionizing radiation, but they are less aware of ionizing radiation use in nuclear medicine studies. They find discussions with radiologists helpful and are concerned about complications of sedation and cost.

High Useful Yield and Isotopic Analysis of Uranium by Resonance Ionization Mass Spectrometry

DOE PAGES

Savina, Michael R.; Isselhardt, Brett H.; Kucher, Andrew; ...

2017-05-09

Useful yields from resonance ionization mass spectrometry can be extremely high compared to other mass spectrometry techniques, but uranium analysis shows strong matrix effects arising from the tendency of uranium to form strongly bound oxide molecules that do not dissociate appreciably on energetic ion bombardment. Here, we demonstrate a useful yield of 24% for metallic uranium. Modeling the laser ionization and ion transmission processes shows that the high useful yield is attributable to a high ion fraction achieved by resonance ionization. We quantify the reduction of uranium oxide surface layers by Ar + and Ga + sputtering. The useful yieldmore » for uranium atoms from a uranium dioxide matrix is 0.4% and rises to 2% when the surface is in sputter equilibrium with the ion beam. The lower useful yield from the oxide is almost entirely due to uranium oxide molecules reducing the neutral atom content of the sputtered flux. We also demonstrate rapid isotopic analysis of solid uranium oxide at a precision of <0.5% relative standard deviation using relatively broadband lasers to mitigate spectroscopic fractionation.« less

High Useful Yield and Isotopic Analysis of Uranium by Resonance Ionization Mass Spectrometry

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

Savina, Michael R.; Isselhardt, Brett H.; Kucher, Andrew

Useful yields from resonance ionization mass spectrometry can be extremely high compared to other mass spectrometry techniques, but uranium analysis shows strong matrix effects arising from the tendency of uranium to form strongly bound oxide molecules that do not dissociate appreciably on energetic ion bombardment. Here, we demonstrate a useful yield of 24% for metallic uranium. Modeling the laser ionization and ion transmission processes shows that the high useful yield is attributable to a high ion fraction achieved by resonance ionization. We quantify the reduction of uranium oxide surface layers by Ar + and Ga + sputtering. The useful yieldmore » for uranium atoms from a uranium dioxide matrix is 0.4% and rises to 2% when the surface is in sputter equilibrium with the ion beam. The lower useful yield from the oxide is almost entirely due to uranium oxide molecules reducing the neutral atom content of the sputtered flux. We also demonstrate rapid isotopic analysis of solid uranium oxide at a precision of <0.5% relative standard deviation using relatively broadband lasers to mitigate spectroscopic fractionation.« less

Efficient ionisation of calcium, strontium and barium by resonant laser pumping

NASA Technical Reports Server (NTRS)

Skinner, C. H.

1980-01-01

Efficient ionization has been observed when an atomic vapor of strontium, barium or calcium was illuminated with a long pulse tunable laser at the frequency of the atomic resonance line. The variation in the degree of ionization with neutral density and laser intensity has been measured using the 'hook' method. The maximum ionization observed was 94%. Excited state populations were measured yielding an excitation temperature (depending on exact experimental conditions) in the region of 0.4 eV. The decay of ion density after the laser pulse was monitored and the recombination coefficients determined. The results are interpreted in terms of an electron heating model.

Abundances, Ionization States, Temperatures, and FIP in Solar Energetic Particles

NASA Astrophysics Data System (ADS)

Reames, Donald V.

2018-04-01

The relative abundances of chemical elements and isotopes have been our most effective tool in identifying and understanding the physical processes that control populations of energetic particles. The early surprise in solar energetic particles (SEPs) was 1000-fold enhancements in {}3He/{}4He from resonant wave-particle interactions in the small "impulsive" SEP events that emit electron beams that produce type III radio bursts. Further studies found enhancements in Fe/O, then extreme enhancements in element abundances that increase with mass-to-charge ratio A/Q, rising by a factor of 1000 from He to Au or Pb arising in magnetic reconnection regions on open field lines in solar jets. In contrast, in the largest SEP events, the "gradual" events, acceleration occurs at shock waves driven out from the Sun by fast, wide coronal mass ejections (CMEs). Averaging many events provides a measure of solar coronal abundances, but A/Q-dependent scattering during transport causes variations with time; thus if Fe scatters less than O, Fe/O is enhanced early and depleted later. To complicate matters, shock waves often reaccelerate impulsive suprathermal ions left over or trapped above active regions that have spawned many impulsive events. Direct measurements of ionization states Q show coronal temperatures of 1-2 MK for most gradual events, but impulsive events often show stripping by matter traversal after acceleration. Direct measurements of Q are difficult and often unavailable. Since both impulsive and gradual SEP events have abundance enhancements that vary as powers of A/Q, we can use abundances to deduce the probable Q-values and the source plasma temperatures during acceleration, ≈3 MK for impulsive SEPs. This new technique also allows multiple spacecraft to measure temperature variations across the face of a shock wave, measurements otherwise unavailable and provides a new understanding of abundance variations in the element He. Comparing coronal abundances from SEPs and from the slow solar wind as a function of the first ionization potential (FIP) of the elements, remaining differences are for the elements C, P, and S. The theory of the fractionation of ions by Alfvén waves shows that C, P, and S are suppressed because of wave resonances during chromospheric transport on closed magnetic loops but not on open magnetic fields that supply the solar wind. Shock waves can accelerate ions from closed coronal loops that easily escape as SEPs, while the solar wind must emerge on open fields.

Influence of ionization on ultrafast gas-based nonlinear fiber optics.

PubMed

Chang, W; Nazarkin, A; Travers, J C; Nold, J; Hölzer, P; Joly, N Y; Russell, P St J

2011-10-10

We numerically investigate the effect of ionization on ultrashort high-energy pulses propagating in gas-filled kagomé-lattice hollow-core photonic crystal fibers by solving an established uni-directional field equation. We consider the dynamics of two distinct regimes: ionization induced blue-shift and resonant dispersive wave emission in the deep-UV. We illustrate how the system evolves between these regimes and the changing influence of ionization. Finally, we consider the effect of higher ionization stages.

Three-photon resonance ionization of atomic Mn in a hot-cavity laser ion source using Ti:sapphire lasers

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

Liu, Y.; Gottwald, T.; Mattolat, C.

We have demonstrated three-photon resonance ionization of atomic manganese (Mn) in a hot-cavity ion source using Ti: sapphire lasers. Three-step ionization schemes employing different intermediate levels and Rydberg or autoionizing (AI) states in the final ionization step are established. Strong AI resonances were observed via the 3d 54s5s f 6S 5/2 level at 49 415.35 cm -1, while Rydberg transitions were reached from the 3d 54s4d e 6D 9/2,7/2,5/2) levels at around 47 210 cm -1. Analyses of the strong Rydberg transitions associated with the 3d 54s4d e 6D 7/2 lower level indicate that they belong to the dipole-allowed 4dmore » → nf 6F° 9/2,7/2,5/2 series converging to the 3d 54s 7S 3 ground state of Mn II. From this series, an ionization potential of 59 959.56 ± 0.01 cm -1 is obtained for Mn. At high ion source temperatures the semi-forbidden 4d → nf 8 F°9/2,7/2,5/2 series was also observed. The overall ionization efficiency for Mn has been measured to be about 0.9% when using the strong AI transition in the third excitation step and 0.3% when employing an intense Rydberg transition. Experimental data indicate that the ionization efficiency was limited by the interaction of Mn atoms with ion source materials at high temperatures.« less

Three-photon resonance ionization of atomic Mn in a hot-cavity laser ion source using Ti:sapphire lasers

DOE PAGES

Liu, Y.; Gottwald, T.; Mattolat, C.; ...

2015-05-08

We have demonstrated three-photon resonance ionization of atomic manganese (Mn) in a hot-cavity ion source using Ti: sapphire lasers. Three-step ionization schemes employing different intermediate levels and Rydberg or autoionizing (AI) states in the final ionization step are established. Strong AI resonances were observed via the 3d 54s5s f 6S 5/2 level at 49 415.35 cm -1, while Rydberg transitions were reached from the 3d 54s4d e 6D 9/2,7/2,5/2) levels at around 47 210 cm -1. Analyses of the strong Rydberg transitions associated with the 3d 54s4d e 6D 7/2 lower level indicate that they belong to the dipole-allowed 4dmore » → nf 6F° 9/2,7/2,5/2 series converging to the 3d 54s 7S 3 ground state of Mn II. From this series, an ionization potential of 59 959.56 ± 0.01 cm -1 is obtained for Mn. At high ion source temperatures the semi-forbidden 4d → nf 8 F°9/2,7/2,5/2 series was also observed. The overall ionization efficiency for Mn has been measured to be about 0.9% when using the strong AI transition in the third excitation step and 0.3% when employing an intense Rydberg transition. Experimental data indicate that the ionization efficiency was limited by the interaction of Mn atoms with ion source materials at high temperatures.« less

Hyperfine Interactions in the Electron Paramagnetic Resonance Spectra of Point Defects in Wide-Band-Gap Semiconductors

DTIC Science & Technology

2014-09-18

compensation) during growth due to their preferred trivalent charge states. The electron paramagnetic resonance spectrum of the singly ionized chromium ...neutral nitrogen acceptor in ZnO . . . . . . . . . . . . . . . . . . 45 16 Spectrum of the singly ionized chromium acceptor in TiO2 . . . . . . . . . 49...is a single crystal of magnesium oxide that has been doped with chromium . Chromium Cr3+ substitutes for magnesium Mg2+ and creates a paramagnetic

Relativistic, correlation, and polarization effects in two-photon photoionization of Xe

NASA Astrophysics Data System (ADS)

Lagutin, B. M.; Petrov, I. D.; Sukhorukov, V. L.; Demekhin, Ph. V.; Knie, A.; Ehresmann, A.

2017-06-01

Two-photon ionization of xenon was investigated theoretically for exciting-photon energies from 6.7 to 11.5 eV, which results in the ionization of Xe between 5 p1 /2 (13.43 eV) and 5 s (23.40 eV) thresholds. We describe the extension of a previously developed computational technique for the inclusion of relativistic effects to calculate energies of intermediate resonance state and cross sections for two-photon ionization. Reasonable consistency of cross sections calculated in length and velocity form was obtained only after considering many-electron correlations. Agreement between calculated and measured resonance energies is found when core polarization was additionally included in the calculations. The presently computed two-photon photoionization cross sections of Xe are compared with Ar cross sections in our previous work. Photoelectron angular distribution parameters calculated here indicate that intermediated resonances strongly influence photoelectron angular distribution of Xe.

Interaction of Strain and Nuclear Spins in Silicon: Quadrupolar Effects on Ionized Donors

NASA Astrophysics Data System (ADS)

Franke, David P.; Hrubesch, Florian M.; Künzl, Markus; Becker, Hans-Werner; Itoh, Kohei M.; Stutzmann, Martin; Hoehne, Felix; Dreher, Lukas; Brandt, Martin S.

2015-07-01

The nuclear spins of ionized donors in silicon have become an interesting quantum resource due to their very long coherence times. Their perfect isolation, however, comes at a price, since the absence of the donor electron makes the nuclear spin difficult to control. We demonstrate that the quadrupolar interaction allows us to effectively tune the nuclear magnetic resonance of ionized arsenic donors in silicon via strain and determine the two nonzero elements of the S tensor linking strain and electric field gradients in this material to S11=1.5 ×1022 V /m2 and S44=6 ×1022 V /m2 . We find a stronger benefit of dynamical decoupling on the coherence properties of transitions subject to first-order quadrupole shifts than on those subject to only second-order shifts and discuss applications of quadrupole physics including mechanical driving of magnetic resonance, cooling of mechanical resonators, and strain-mediated spin coupling.

The laser and optical system for the RIBF-PALIS experiment

NASA Astrophysics Data System (ADS)

Sonoda, T.; Iimura, H.; Reponen, M.; Wada, M.; Katayama, I.; Sonnenschein, V.; Takamatsu, T.; Tomita, H.; Kojima, T. M.

2018-01-01

This paper describes the laser and optical system for the Parasitic radioactive isotope (RI) beam production by Laser Ion-Source (PALIS) in the RIKEN fragment separator facility. This system requires an optical path length of 70 m for transporting the laser beam from the laser light source to the place for resonance ionization. To accomplish this, we designed and implemented a simple optical system consisting of several mirrors equipped with compact stepping motor actuators, lenses, beam spot screens and network cameras. The system enables multi-step laser resonance ionization in the gas cell and gas jet via overlap with a diameter of a few millimeters, between the laser photons and atomic beam. Despite such a long transport distance, we achieved a transport efficiency for the UV laser beam of about 50%. We also confirmed that the position stability of the laser beam stays within a permissible range for dedicated resonance ionization experiments.

Optimal control of the strong-field ionization of silver clusters in helium droplets

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

Truong, N. X.; Goede, S.; Przystawik, A.

Optimal control techniques combined with femtosecond laser pulse shaping are applied to steer and enhance the strong-field induced emission of highly charged atomic ions from silver clusters embedded in helium nanodroplets. With light fields shaped in amplitude and phase we observe a substantial increase of the Ag{sup q+} yield for q>10 when compared to bandwidth-limited and optimally stretched pulses. A remarkably simple double-pulse structure, containing a low-intensity prepulse and a stronger main pulse, turns out to produce the highest atomic charge states up to Ag{sup 20+}. A negative chirp during the main pulse hints at dynamic frequency locking to themore » cluster plasmon. A numerical optimal control study on pure silver clusters with a nanoplasma model converges to a similar pulse structure and corroborates that the optimal light field adapts to the resonant excitation of cluster surface plasmons for efficient ionization.« less

High-resolution multimodal clinical multiphoton tomography of skin

NASA Astrophysics Data System (ADS)

König, Karsten

2011-03-01

This review focuses on multimodal multiphoton tomography based on near infrared femtosecond lasers. Clinical multiphoton tomographs for 3D high-resolution in vivo imaging have been placed into the market several years ago. The second generation of this Prism-Award winning High-Tech skin imaging tool (MPTflex) was introduced in 2010. The same year, the world's first clinical CARS studies have been performed with a hybrid multimodal multiphoton tomograph. In particular, non-fluorescent lipids and water as well as mitochondrial fluorescent NAD(P)H, fluorescent elastin, keratin, and melanin as well as SHG-active collagen has been imaged with submicron resolution in patients suffering from psoriasis. Further multimodal approaches include the combination of multiphoton tomographs with low-resolution wide-field systems such as ultrasound, optoacoustical, OCT, and dermoscopy systems. Multiphoton tomographs are currently employed in Australia, Japan, the US, and in several European countries for early diagnosis of skin cancer, optimization of treatment strategies, and cosmetic research including long-term testing of sunscreen nanoparticles as well as anti-aging products.

Application of Negative Curvature Hollow-Core Fiber in an Optical Fiber Sensor Setup for Multiphoton Spectroscopy

PubMed Central

Stawska, Hanna Izabela; Mazur, Leszek Mateusz; Kosolapov, Alexey; Kolyadin, Anton; Bereś-Pawlik, Elżbieta

2017-01-01

In this paper, an application of negative curvature hollow core fiber (NCHCF) in an all-fiber, multiphoton fluorescence sensor setup is presented. The dispersion parameter (D) of this fiber does not exceed the value of 5 ps/nm × km across the optical spectrum of (680–750) nm, making it well suited for the purpose of multiphoton excitation of biological fluorophores. Employing 1.5 m of this fiber in a simple, all-fiber sensor setup allows us to perform multiphoton experiments without any dispersion compensation methods. Multiphoton excitation of nicotinamide adenine dinucleotide (NADH) and flavin adenine dinucleotide (FAD) with this fiber shows a 6- and 9-fold increase, respectively, in the total fluorescence signal collected when compared with the commercial solution in the form of a hollow-core photonic band gap fiber (HCPBF). To the author’s best knowledge, this is the first time an NCHCF was used in an optical-fiber sensor setup for multiphoton fluorescence experiments. PMID:28984838

Application of Negative Curvature Hollow-Core Fiber in an Optical Fiber Sensor Setup for Multiphoton Spectroscopy.

PubMed

Popenda, Maciej Andrzej; Stawska, Hanna Izabela; Mazur, Leszek Mateusz; Jakubowski, Konrad; Kosolapov, Alexey; Kolyadin, Anton; Bereś-Pawlik, Elżbieta

2017-10-06

In this paper, an application of negative curvature hollow core fiber (NCHCF) in an all-fiber, multiphoton fluorescence sensor setup is presented. The dispersion parameter (D) of this fiber does not exceed the value of 5 ps/nm × km across the optical spectrum of (680-750) nm, making it well suited for the purpose of multiphoton excitation of biological fluorophores. Employing 1.5 m of this fiber in a simple, all-fiber sensor setup allows us to perform multiphoton experiments without any dispersion compensation methods. Multiphoton excitation of nicotinamide adenine dinucleotide (NADH) and flavin adenine dinucleotide (FAD) with this fiber shows a 6- and 9-fold increase, respectively, in the total fluorescence signal collected when compared with the commercial solution in the form of a hollow-core photonic band gap fiber (HCPBF). To the author's best knowledge, this is the first time an NCHCF was used in an optical-fiber sensor setup for multiphoton fluorescence experiments.

Strong-Field Control of Laser Filamentation Mechanisms

NASA Astrophysics Data System (ADS)

Levis, Robert; Romanov, Dmitri; Filin, Aleskey; Compton, Ryan

2008-05-01

The propagation of short strong-file laser pulses in gas and solution phases often result in formation of filaments. This phenomenon involves many nonlinear processes including Kerr lensing, group velocity dispersion, multi-photon ionization, plasma defocusing, intensity clamping, and self-steepening. Of these, formation and dynamics of pencil-shape plasma areas plays a crucial role. The fundamental understanding of these laser-induced plasmas requires additional effort, because the process is highly nonlinear and complex. We studied the ultrafast laser-generated plasma dynamics both experimentally and theoretically. Ultrafast plasma dynamics was probed using Coherent Anti-Stokes Raman Scattering. The measurements were made in a room temperature gas maintained at 1 atm in a flowing cell. The time dependent scattering was measured by delaying the CARS probe with respect to the intense laser excitation pulse. A general trend is observed between the spacing of the ground state and the first allowed excited state with the rise time for the noble gas series and the molecular gases. This trend is consistent with our theoretical model, which considers the ultrafast dynamics of the strong field generated plasma as a three-step process; (i) strong-field ionization followed by the electron gaining considerable kinetic energy during the pulse; (ii) immediate post-pulse dynamics: fast thermalization, impact-ionization-driven electron multiplication and cooling; (iii) ensuing relaxation: evolution to electron-ion equilibrium and eventual recombination.

Toward Rotational State-Selective Photoionization of ThF+ Ions

NASA Astrophysics Data System (ADS)

Zhou, Yan; Ng, Kia Boon; Gresh, Dan; Cairncross, William; Grau, Matt; Ni, Yiqi; Cornell, Eric; Ye, Jun

2016-06-01

ThF+ has been chosen to replace HfF+ for a second-generation measurement of the electric dipole moment of the electron (eEDM). Compared to the currently running HfF+ eEDM experiment, ThF+ has several advantages: (i) the eEDM-sensitive state (3Δ1) is the ground state, which facilitates a long coherence time [1]; (ii) its effective electric field (35 GV/cm) is 50% larger than that of HfF+, which promises a direct increase of the eEDM sensitivity [2]; and (iii) the ionization energy of neutral ThF is lower than its dissociation energy, which introduces greater flexibility in rotational state-selective photoionization via core-nonpenetrating Rydberg states [3]. In this talk, we first present our strategy of preparing and utilizing core-nonpenetrating Rydberg states for rotational state-selective ionization. Then, we report spectroscopic data of laser-induced fluorescence of neutral ThF, which provides critical information for multi-photon ionization spectroscopy. [1] D. N. Gresh, K. C. Cossel, Y. Zhou, J. Ye, E. A. Cornell, Journal of Molecular Spectroscopy, 319 (2016), 1-9 [2] M. Denis, M. S. Nørby, H. J. A. Jensen, A. S. P. Gomes, M. K. Nayak, S. Knecht, T. Fleig, New Journal of Physics, 17 (2015) 043005. [3] Z. J. Jakubek, R. W. Field, Journal of Molecular Spectroscopy 205 (2001) 197-220.

Local ablation therapy with contrast-enhanced ultrasonography for hepatocellular carcinoma: a practical review

PubMed Central

Kim, Tae Kyoung; Khalili, Korosh; Jang, Hyun-Jung

2015-01-01

A successful program for local ablation therapy for hepatocellular carcinoma (HCC) requires extensive imaging support for diagnosis and localization of HCC, imaging guidance for the ablation procedures, and post-treatment monitoring. Contrast-enhanced ultrasonography (CEUS) has several advantages over computed tomography/magnetic resonance imaging (CT/MRI), including real-time imaging capability, sensitive detection of arterial-phase hypervascularity and washout, no renal excretion, no ionizing radiation, repeatability, excellent patient compliance, and relatively low cost. CEUS is useful for image guidance for isoechoic lesions. While contrast-enhanced CT/MRI is the standard method for the diagnosis of HCC and post-ablation monitoring, CEUS is useful when CT/MRI findings are indeterminate or CT/MRI is contraindicated. This article provides a practical review of the role of CEUS in imaging algorithms for pre- and post-ablation therapy for HCC. PMID:26169081

Exploration of the Memory Effect on the Photon-Assisted Tunneling via a Single Quantum Dot:. a Generalized Floquet Theoretical Approach

NASA Astrophysics Data System (ADS)

Chen, Hsing-Ta; Ho, Tak-San; Chu, Shih-I.

The generalized Floquet approach is developed to study memory effect on electron transport phenomena through a periodically driven single quantum dot in an electrode-multi-level dot-electrode nanoscale quantum device. The memory effect is treated using a multi-function Lorentzian spectral density (LSD) model that mimics the spectral density of each electrode in terms of multiple Lorentzian functions. For the symmetric single-function LSD model involving a single-level dot, the underlying single-particle propagator is shown to be related to a 2×2 effective time-dependent Hamiltonian that includes both the periodic external field and the electrode memory effect. By invoking the generalized Van Vleck (GVV) nearly degenerate perturbation theory, an analytical Tien-Gordon-like expression is derived for arbitrary order multi-photon resonance d.c. tunneling current. Numerically converged simulations and the GVV analytical results are in good agreement, revealing the origin of multi-photon coherent destruction of tunneling and accounting for the suppression of the staircase jumps of d.c. current due to the memory effect. Specially, a novel blockade phenomenon is observed, showing distinctive oscillations in the field-induced current in the large bias voltage limit.

Cellular organization and spectral diversity of GFP-like proteins in live coral cells studied by single and multiphoton imaging and microspectroscopy

NASA Astrophysics Data System (ADS)

Salih, Anya; Cox, Guy C.; Larkum, Anthony W.

2003-07-01

Tissues of many marine invertebrates of class Anthozoa contain intensely fluorescent or brightly coloured pigments. These pigments belong to a family of photoactive proteins closely related to Green Fluorescent Protein (GFP), and their emissions range from blue to red wavelengths. The great diversity of these pigments has only recently been realised. To investigate the role of these proteins in corals, we have performed an in vivo fluorescent pigment (FP) spectral and cellular distribution analyses in live coral cells using single and multi-photon laser scanning imaging and microspectroscopy. These analyses revealed that even single colour corals contain spectroscopically heterogeneous pigment mixtures, with 2-5 major colour types in the same area of tissue. They were typically arranged in step-wise light emission energy gradients (e.g. blue, green, yellow, red). The successive overlapping emission-excitation spectral profiles of differently coloured FPs suggested that they were suited for sequential energy coupling. Traces of red FPs (emission = 570-660 nm) were present, even in non-red corals. We confirmed that radiative energy transfer could occur between separate granules of blue and green FPs and that energy transfer was inversely proportional to the square of the distance between them. Multi-photon micro-spectrofluorometric analysis gave significantly improved spectral resolution by restricting FP excitation to a single point in the focal plane of the sample. Pigment heterogeneity at small scales within granules suggested that fluorescence resonance energy transfer (FRET) might be occurring, and we confirmed that this was the case. Thus, energy transfer can take place both radiatively and by FRET, probably functioning in photoprotection by dissipation of excessive solar radiation.

Multiphoton dissociation and thermal unimolecular reactions induced by infrared lasers. [REAMPA code

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

Dai, H.L.

1981-04-01

Multiphoton dissociation (MPD) of ethyl chloride was studied using a tunable 3.3 ..mu..m laser to excite CH stretches. The absorbed energy increases almost linearly with fluence, while for 10 ..mu..m excitation there is substantial saturation. Much higher dissociation yields were observed for 3.3 ..mu..m excitation than for 10 ..mu..m excitation, reflecting bottlenecking in the discrete region of 10 ..mu..m excitation. The resonant nature of the excitation allows the rate equations description for transitions in the quasicontinuum and continuum to be extended to the discrete levels. Absorption cross sections are estimated from ordinary ir spectra. A set of cross sections whichmore » is constant or slowly decreasing with increasing vibrational excitation gives good fits to both absorption and dissociation yield data. The rate equations model was also used to quantitatively calculate the pressure dependence of the MPD yield of SF/sub 6/ caused by vibrational self-quenching. Between 1000-3000 cm/sup -1/ of energy is removed from SF/sub 6/ excited to approx. > 60 kcal/mole by collision with a cold SF/sub 6/ molecule at gas kinetic rate. Calculation showed the fluence dependence of dissociation varies strongly with the gas pressure. Infrared multiphoton excitation was applied to study thermal unimolecular reactions. With SiF/sub 4/ as absorbing gas for the CO/sub 2/ laser pulse, transient high temperature pulses were generated in a gas mixture. IR fluorescence from the medium reflected the decay of the temperature. The activation energy and the preexponential factor of the reactant dissociation were obtained from a phenomenological model calculation. Results are presented in detail. (WHK)« less

Compton spectra of atoms at high x-ray intensity

NASA Astrophysics Data System (ADS)

Son, Sang-Kil; Geffert, Otfried; Santra, Robin

2017-03-01

Compton scattering is the nonresonant inelastic scattering of an x-ray photon by an electron and has been used to probe the electron momentum distribution in gas-phase and condensed-matter samples. In the low x-ray intensity regime, Compton scattering from atoms dominantly comes from bound electrons in neutral atoms, neglecting contributions from bound electrons in ions and free (ionized) electrons. In contrast, in the high x-ray intensity regime, the sample experiences severe ionization via x-ray multiphoton multiple ionization dynamics. Thus, it becomes necessary to take into account all the contributions to the Compton scattering signal when atoms are exposed to high-intensity x-ray pulses provided by x-ray free-electron lasers (XFELs). In this paper, we investigate the Compton spectra of atoms at high x-ray intensity, using an extension of the integrated x-ray atomic physics toolkit, xatom. As the x-ray fluence increases, there is a significant contribution from ionized electrons to the Compton spectra, which gives rise to strong deviations from the Compton spectra of neutral atoms. The present study provides not only understanding of the fundamental XFEL-matter interaction but also crucial information for single-particle imaging experiments, where Compton scattering is no longer negligible. , which features invited work from the best early-career researchers working within the scope of J. Phys. B. This project is part of the Journal of Physics series’ 50th anniversary celebrations in 2017. Sang-Kil Son was selected by the Editorial Board of J. Phys. B as an Emerging Leader.

Polarization Enhanced Charge Transfer: Dual-Band GaN-Based Plasmonic Photodetector.

PubMed

Jia, Ran; Zhao, Dongfang; Gao, Naikun; Liu, Duo

2017-01-13

Here, we report a dual-band plasmonic photodetector based on Ga-polar gallium nitride (GaN) for highly sensitive detection of UV and green light. We discover that decoration of Au nanoparticles (NPs) drastically increases the photoelectric responsivities by more than 50 times in comparition to the blank GaN photodetector. The observed behaviors are attributed to polarization enhanced charge transfer of optically excited hot electrons from Au NPs to GaN driven by the strong spontaneous polarization field of Ga-polar GaN. Moreover, defect ionization promoted by localized surface plasmon resonances (LSPRs) is also discussed. This novel type of photodetector may shed light on the design and fabrication of photoelectric devices based on polar semiconductors and microstructural defects.

Ultrafast Phenomena 6. Proceedings of the International Conference (6th) Held in Kyoto, Japan on July 12-15, 1988. Springer Series in Chemical Physics, Volume 48

DTIC Science & Technology

1988-01-01

affected mainly by those of upper- and lower-side stacks, respectively. In the region of the wave- length longer than the resonance wavelength AAO of the...multiphoton processes in a solid aluminum target produce an aluminum ion plasma exhibiting line radiation at energies exceeding 2 keV. Another experiment...voltages of the tube photocathode and mesh were -8kV, -3kV respectively relative to the grounded anode . This gave, for a mesh to cathode spacing of 1.2mm

Potential scattering in the presence of a static magnetic field and a radiation field of arbitrary polarization

NASA Astrophysics Data System (ADS)

Ferrante, G.; Zarcone, M.; Nuzzo, S.; McDowell, M. R. C.

1982-05-01

Expressions are obtained for the total cross sections for scattering of a charged particle by a potential in the presence of a static uniform magnetic field and a radiation field of arbitrary polarization. For a Coulomb field this is closely related to the time reverse of photoionization of a neutral atom in a magnetic field, including multiphoton effects off-resonance. The model is not applicable when the radiation energy approaches one of the quasi-Landau state separations. The effects of radiation field polarization are examined in detail.

Ultrastrong Coupling Few-Photon Scattering Theory

NASA Astrophysics Data System (ADS)

Shi, Tao; Chang, Yue; García-Ripoll, Juan José

2018-04-01

We study the scattering of individual photons by a two-level system ultrastrongly coupled to a waveguide. The scattering is elastic for a broad range of couplings and can be described with an effective U (1 )-symmetric Hamiltonian. This simple model allows the prediction of scattering resonance line shapes, validated up to α =0.3 , and close to the Toulouse point α =1 /2 , where inelastic scattering becomes relevant. Our predictions model experiments with superconducting circuits [P. Forn-Díaz et al., Nat. Phys. 13, 39 (2017), 10.1038/nphys3905] and can be extended to study multiphoton scattering.

Ultrastrong Coupling Few-Photon Scattering Theory.

PubMed

Shi, Tao; Chang, Yue; García-Ripoll, Juan José

2018-04-13

We study the scattering of individual photons by a two-level system ultrastrongly coupled to a waveguide. The scattering is elastic for a broad range of couplings and can be described with an effective U(1)-symmetric Hamiltonian. This simple model allows the prediction of scattering resonance line shapes, validated up to α=0.3, and close to the Toulouse point α=1/2, where inelastic scattering becomes relevant. Our predictions model experiments with superconducting circuits [P. Forn-Díaz et al., Nat. Phys. 13, 39 (2017)NPAHAX1745-247310.1038/nphys3905] and can be extended to study multiphoton scattering.

Identification of four rotamers of m-methoxystyrene by resonant two-photon ionization and mass analyzed threshold ionization spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Yanqi; Tzeng, Sheng Yuan; Shivatare, Vidya; Takahashi, Kaito; Zhang, Bing; Tzeng, Wen Bih

2015-03-01

We report the vibronic and cation spectra of four rotamers of m-methoxystyrene, recorded by using the two-color resonant two-photon ionization and mass-analyzed threshold ionization techniques. The excitation energies of the S1← S0 electronic transition are found to be 32 767, 32 907, 33 222, and 33 281 cm-1, and the corresponding adiabatic ionization energies are 65 391, 64 977, 65 114, and 64 525 cm-1 for these isomeric species. Most of the observed active vibrations in the electronically excited S1 and cationic ground D0 states involve in-plane ring deformation and substituent-sensitive bending motions. It is found that the relative orientation of the methoxyl with respect to the vinyl group does not influence the vibrational frequencies of the ring-substituent bending modes. The two dimensional potential energy surface calculations support our experimental finding that the isomerization is restricted in the S1 and D0 states.

Resonance Ionization Mass Spectrometry System for Measurement of Environmental Samples

NASA Astrophysics Data System (ADS)

Pibida, L.; McMahon, C. A.; Nörtershäuser, W.; Bushaw, B. A.

2002-10-01

A resonance ionization mass spectrometry (RIMS) system has been developed at the National Institute of Standards and Technology (NIST) for sensitive and selective determination of radio-cesium in the environment. The overall efficiency was determined to be 4×10-7 with a combined (laser and mass spectrometer) selectivity of 108 for both 135Cs and 137Cs with respect to 133Cs. RIMS isotopic ratio measurements of 135Cs/ 137Cs were performed on a nuclear fuel burn-up sample and compared to measurements on a similar system at Pacific Northwest National Laboratory (PNNL) and to conventional thermal ionization mass spectrometry (TIMS). Results of preliminary RIMS investigations on a freshwater lake sediment sample are also discussed.

QED theory of multiphoton transitions in atoms and ions

NASA Astrophysics Data System (ADS)

Zalialiutdinov, Timur A.; Solovyev, Dmitry A.; Labzowsky, Leonti N.; Plunien, Günter

2018-03-01

This review surveys the quantum theory of electromagnetic radiation for atomic systems. In particular, a review of current theoretical studies of multiphoton processes in one and two-electron atoms and highly charged ions is provided. Grounded on the quantum electrodynamics description the multiphoton transitions in presence of cascades, spin-statistic behaviour of equivalent photons and influence of external electric fields on multiphoton in atoms and anti-atoms are discussed. Finally, the nonresonant corrections which define the validity of the concept of the excited state energy levels are introduced.

Wavefront sensorless adaptive optics temporal focusing-based multiphoton microscopy

PubMed Central

Chang, Chia-Yuan; Cheng, Li-Chung; Su, Hung-Wei; Hu, Yvonne Yuling; Cho, Keng-Chi; Yen, Wei-Chung; Xu, Chris; Dong, Chen Yuan; Chen, Shean-Jen

2014-01-01

Temporal profile distortions reduce excitation efficiency and image quality in temporal focusing-based multiphoton microscopy. In order to compensate the distortions, a wavefront sensorless adaptive optics system (AOS) was integrated into the microscope. The feedback control signal of the AOS was acquired from local image intensity maximization via a hill-climbing algorithm. The control signal was then utilized to drive a deformable mirror in such a way as to eliminate the distortions. With the AOS correction, not only is the axial excitation symmetrically refocused, but the axial resolution with full two-photon excited fluorescence (TPEF) intensity is also maintained. Hence, the contrast of the TPEF image of a R6G-doped PMMA thin film is enhanced along with a 3.7-fold increase in intensity. Furthermore, the TPEF image quality of 1μm fluorescent beads sealed in agarose gel at different depths is improved. PMID:24940539

Improvement of axial excitation confinement in temporal focusing-based multiphoton microscopy via spatially modulated illumination

NASA Astrophysics Data System (ADS)

Chang, Chia-Yuan; Chen, Shean-Jen

2017-02-01

Conventional temporal focusing-based multiphoton excitation microscopy (TFMPEM) can offer widefield optical sectioning with an axial excitation confinement (AEC) of a few microns. Herein, a developed TFMPEM with a digital micromirror device (DMD), acting as the blazed grating for light spatial dispersion and simultaneous patterned illumination, has been extended to implement spatially modulated illumination at structured frequency and orientation. By implementing the spatially modulated illumination, the beam coverage at the back-focal aperture of the objective lens can be increased. As a result, the AEC can be condensed from 3.0 μm to 1.5 μm in full width at half maximum for a 2-fold enhancement. Furthermore, by using HiLo microscopy with two structured illuminations at the same spatial frequency but different orientation, biotissue images according to the structured illumination with condensed AEC is obviously superior in contrast and scattering suppression.

Multiphoton microscopy guides neurotrophin modification with poly(ethylene glycol) to enhance interstitial diffusion

NASA Astrophysics Data System (ADS)

Stroh, Mark; Zipfel, Warren R.; Williams, Rebecca M.; Ma, Shu Chin; Webb, Watt W.; Saltzman, W. Mark

2004-07-01

Brain-derived neurotrophic factor (BDNF) is a promising therapeutic agent for the treatment of neurodegenerative diseases. However, the limited distribution of this molecule after administration into the brain tissue considerably hampers its efficacy. Here, we show how multiphoton microscopy of fluorescently tagged BDNF in brain-tissue slices provides a useful and rapid screening method for examining the diffusion of large molecules in tissues, and for studying the effects of chemical modifications-for example, conjugating with polyethylene glycol (PEG)-on the diffusion constant. This single variable, obtained by monitoring short-term diffusion in real time, can be effectively used for rational drug design. In this study on fluorescently tagged BDNF and BDNF-PEG, we identify slow diffusion as a major contributing factor to the limited penetration of BDNF, and demonstrate how chemical modification can be used to overcome this barrier.

Sequential double photodetachment of He- in elliptically polarized laser fields

NASA Astrophysics Data System (ADS)

Génévriez, Matthieu; Dunseath, Kevin M.; Terao-Dunseath, Mariko; Urbain, Xavier

2018-02-01

Four-photon double detachment of the helium negative ion is investigated experimentally and theoretically for photon energies where the transient helium atom is in the 1 s 2 s 3S or 1 s 2 p P3o states, which subsequently ionize by absorption of three photons. Ionization is enhanced by intermediate resonances, giving rise to series of peaks in the He+ spectrum, which we study in detail. The He+ yield is measured in the wavelength ranges from 530 to 560 nm and from 685 to 730 nm and for various polarizations of the laser light. Double detachment is treated theoretically as a sequential process, within the framework of R -matrix theory for the first step and effective Hamiltonian theory for the second step. Experimental conditions are accurately modeled, and the measured and simulated yields are in good qualitative and, in some cases, quantitative agreement. Resonances in the double detachment spectra can be attributed to well-defined Rydberg states of the transient atom. The double detachment yield exhibits a strong dependence on the laser polarization which can be related to the magnetic quantum number of the intermediate atomic state. We also investigate the possibility of nonsequential double detachment with a two-color experiment but observe no evidence for it.

Laser microprobe and resonant laser ablation for depth profile measurements of hydrogen isotope atoms contained in graphite.

PubMed

Yorozu, M; Yanagida, T; Nakajyo, T; Okada, Y; Endo, A

2001-04-20

We measured the depth profile of hydrogen atoms in graphite by laser microprobing combined with resonant laser ablation. Deuterium-implanted graphite was employed for the measurements. The sample was ablated by a tunable laser with a wavelength corresponding to the resonant wavelength of 1S-2S of deuterium with two-photon excitation. The ablated deuterium was ionized by a 2 + 1 resonant ionization process. The ions were analyzed by a time-of-flight mass spectrometer. The deuterium ions were detected clearly with the resonant ablation. The detection limit was estimated to be less than 10(16) atoms/cm(3) in our experiments. We determined the depth profile by considering the etching profile and the etching rate. The depth profile agreed well with Monte Carlo simulations to within a precision of 23 mum for the center position and 4-mum precision for distributions for three different implantation depths.

Enzyme-substrate and enzyme-inhibitor complexes of triose phosphate isomerase studied by 31P nuclear magnetic resonance.

PubMed Central

Campbell, I D; Jones, R B; Kiener, P A; Waley, S G

1979-01-01

The complex formed between the enzyme triose phosphate isomerase (EC 5.3.1.1.), from rabbit and chicken muscle, and its substrate dihydroxyacetone phosphate was studied by 31P n.m.r. Two other enzyme-ligant complexes examined were those formed by glycerol 3-phosphate (a substrate analogue) and by 2-phosphoglycollate (potential transition-state analogue). Separate resonances were observed in the 31P n.m.r. spectrum for free and bound 2-phosphoglycollate, and this sets an upper limit to the rate constant for dissociation of the enzyme-inhibitor complex; the linewidth of the resonance assigned to the bound inhibitor provided further kinetic information. The position of this resonance did not vary with pH but remained close to that of the fully ionized form of the free 2-phosphoglycollate. It is the fully ionized form of this ligand that binds to the enzyme. The proton uptake that accompanies binding shows protonation of a group on the enzyme. On the basis of chemical and crystallographic information [Hartman (1971) Biochemistry 10, 146--154; Miller & Waley (1971) Biochem. J. 123, 163--170; De la Mare, Coulson, Knowles, Priddle & Offord )1972) Biochem. J. 129, 321--331; Phillips, Rivers, Sternberg, Thornton & Wilson (1977) Biochem. Soc. Trans. 5, 642--647] this group is believed to be glutamate-165. On the other hand, the position of the resonance of D-glycerol 3 phosphate (sn-glycerol 1-phosphate) in the enzyme-ligand complex changes with pH, and both monoanion and dianon of the ligand bind, although dianion binds better. The substrate, dihydroxyacetone phosphate, behaves essentially like glycerol 3-phosphate. The experiments with dihydroxy-acetone phosphate and triose phosphate isomerase have to be carried out at 1 degree C because at 37 degrees C there is conversion into methyl glyoxal and orthophosphate. The mechanismof the enzymic reaction and the reasons for rate-enhancement are considered, and aspects of the pH-dependence are discussed in an Appendix. PMID:38777

Coherent control of photoelectron wavepacket angular interferograms

NASA Astrophysics Data System (ADS)

Hockett, P.; Wollenhaupt, M.; Baumert, T.

2015-11-01

Coherent control over photoelectron wavepackets, via the use of polarization-shaped laser pulses, can be understood as a time and polarization-multiplexed process, where the final (time-integrated) observable coherently samples all instantaneous states of the light-matter interaction. In this work, we investigate this multiplexing via computation of the observable photoelectron angular interferograms resulting from multi-photon atomic ionization with polarization-shaped laser pulses. We consider the polarization sensitivity of both the instantaneous and cumulative continuum wavefunction; the nature of the coherent control over the resultant photoelectron interferogram is thus explored in detail. Based on this understanding, the use of coherent control with polarization-shaped pulses as a methodology for a highly multiplexed coherent quantum metrology is also investigated, and defined in terms of the information content of the observable.

Self-channeling of high-power laser pulses through strong atmospheric turbulence

NASA Astrophysics Data System (ADS)

Peñano, J.; Palastro, J. P.; Hafizi, B.; Helle, M. H.; DiComo, G. P.

2017-07-01

We present an unusual example of truly long-range propagation of high-power laser pulses through strong atmospheric turbulence. A form of nonlinear self-channeling is achieved when the laser power is close to the self-focusing power of air and the transverse dimensions of the pulse are smaller than the coherence diameter of turbulence. In this mode, nonlinear self-focusing counteracts diffraction, and turbulence-induced spreading is greatly reduced. Furthermore, the laser intensity is below the ionization threshold so that multiphoton absorption and plasma defocusing are avoided. Simulations show that the pulse can propagate many Rayleigh lengths (several kilometers) while maintaining a high intensity. In the presence of aerosols, or other extinction mechanisms that deplete laser energy, the pulse can be chirped to maintain the channeling.

Selected cis- and trans-3-fluorostyrene rotamers studied by two-color resonant two-photon mass-analyzed threshold ionization spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Pei Ying; Tzeng, Wen Bih

2015-10-01

We applied two-color resonant two-photon ionization and mass-analyzed threshold ionization techniques to record the vibronic, photoionization efficiency, and cation spectra of the selected rotamers of 3-fluorostyrene. The adiabatic ionization energies of cis- and trans-3-fluorostyrene were determined to be 69 960 ± 5 and 69 856 ± 5 cm-1, respectively. Cation vibrations 10a, 15, 6b, and 12 of both rotamers have been found to have frequencies of 218, 404, 452, and 971 cm-1, respectively. This finding shows that the relative orientation of the vinyl group with respect to the F atom does not affect these vibrations of the 3-fluorostyrene cation. Our one-dimensional potential energy surface calculations support that the cis-trans isomerization of 3-fluorostyrene does not occur under the present experimental conditions.

Current developments in clinical multiphoton tomography

NASA Astrophysics Data System (ADS)

König, Karsten; Weinigel, Martin; Breunig, Hans Georg; Gregory, Axel; Fischer, Peter; Kellner-Höfer, Marcel; Bückle, Rainer

2010-02-01

Two-photon microscopy has been introduced in 1990 [1]. 13 years later, CE-marked clinical multiphoton systems for 3D imaging of human skin with subcellular resolution have been launched by the JenLab company with the tomograph DermaInspectTM. In 2010, the second generation of clinical multiphoton tomographs was introduced. The novel mobile multiphoton tomograph MPTflexTM, equipped with a flexible articulated optical arm, provides an increased flexibility and accessibility especially for clinical and cosmetical examinations. The multiphoton excitation of fluorescent biomolecules like NAD(P)H, flavins, porphyrins, elastin, and melanin as well as the second harmonic generation of collagen is induced by picojoule femtosecond laser pulses from an tunable turn-key near infrared laser system. The ability for rapid highquality image acquisition, the user-friendly operation of the system, and the compact and flexible design qualifies this system to be used for melanoma detection, diagnostics of dermatological disorders, cosmetic research, and skin aging measurements as well as in situ drug monitoring and animal research. So far, more than 1,000 patients and volunteers have been investigated with the multiphoton tomographs in Europe, Asia, and Australia.

Amplitudes for multiphoton quantum processes in linear optics

NASA Astrophysics Data System (ADS)

Urías, Jesús

2011-07-01

The prominent role that linear optical networks have acquired in the engineering of photon states calls for physically intuitive and automatic methods to compute the probability amplitudes for the multiphoton quantum processes occurring in linear optics. A version of Wick's theorem for the expectation value, on any vector state, of products of linear operators, in general, is proved. We use it to extract the combinatorics of any multiphoton quantum processes in linear optics. The result is presented as a concise rule to write down directly explicit formulae for the probability amplitude of any multiphoton process in linear optics. The rule achieves a considerable simplification and provides an intuitive physical insight about quantum multiphoton processes. The methodology is applied to the generation of high-photon-number entangled states by interferometrically mixing coherent light with spontaneously down-converted light.

Invited Review Article: Imaging techniques for harmonic and multiphoton absorption fluorescence microscopy

PubMed Central

Carriles, Ramón; Schafer, Dawn N.; Sheetz, Kraig E.; Field, Jeffrey J.; Cisek, Richard; Barzda, Virginijus; Sylvester, Anne W.; Squier, Jeffrey A.

2009-01-01

We review the current state of multiphoton microscopy. In particular, the requirements and limitations associated with high-speed multiphoton imaging are considered. A description of the different scanning technologies such as line scan, multifoci approaches, multidepth microscopy, and novel detection techniques is given. The main nonlinear optical contrast mechanisms employed in microscopy are reviewed, namely, multiphoton excitation fluorescence, second harmonic generation, and third harmonic generation. Techniques for optimizing these nonlinear mechanisms through a careful measurement of the spatial and temporal characteristics of the focal volume are discussed, and a brief summary of photobleaching effects is provided. Finally, we consider three new applications of multiphoton microscopy: nonlinear imaging in microfluidics as applied to chemical analysis and the use of two-photon absorption and self-phase modulation as contrast mechanisms applied to imaging problems in the medical sciences. PMID:19725639

Photoproduction of Mesons

NASA Astrophysics Data System (ADS)

Schmieden, Hartmut; Klein, Friedrich

2017-01-01

B.1 is one of the experimental projects within the CRC16. It aims at the systematic investigation of the photoproduction of mesons off nucleons in order to understand reaction mechanisms and the relevant degrees of freedom in resonance formation. Of particular interest is the photoproduction of mesons heavier than the pion and resonances involving hidden or open strangeness. Essential hardware contributions have been made to the experimental programme of the CRC16 through tagging systems, and photon-beam polarisation and polarimetry. A new experiment has been set up within the framework of the BGO-OD collaboration. This combines a forward magnetic spectrometer with a central BGO calorimeter with charged particle recognition and identification. The BGO-OD experiment enables reconstruction of complex final states composed of both charged and neutral particles, complementary to the existing CBELSA/TAPS calorimeter which is optimised for multi-photon final states. Selected results of the 12-year CRC period are presented from both experiments.

New Insights into the Mechanism Underlying the Synergistic Action of Ionizing Radiation With Platinum Chemotherapeutic Drugs: The Role of Low-Energy Electrons

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

Rezaee, Mohammad, E-mail: Mohammad.Rezaee@USherbrooke.ca; Hunting, Darel John; Sanche, Léon

Purpose: To investigate the efficiencies of platinum chemotherapeutic drugs (Pt-drugs) in the sensitization of DNA to the direct effects of ionizing radiation and to determine the role of low-energy electrons (LEEs) in this process. Methods and Materials: Complexes of supercoiled plasmid DNA covalently bound to either cisplatin, carboplatin, or oxaliplatin were prepared in different molar ratios. Solid films of DNA and DNA modified by Pt-drugs were irradiated with either 10-KeV or 10-eV electrons. Damages to DNA were quantified by gel electrophoresis, and the yields for damage formation were obtained from exposure–response curves. Results: The presence of an average of 2more » Pt-drug–DNA adducts (Pt-adducts) in 3199-bp plasmid DNA increases the probability of a double-strand break by factors of 3.1, 2.5, and 2.4 for carboplatin, cisplatin, and oxaliplatin, respectively. Electrons with energies of 10 eV and 10 KeV interact with Pt-adducts to preferentially enhance the formation of cluster lesions. The maximum increase in radiosensitivity per Pt-adduct is found at ratios up to 3.1 × 10{sup −4} Pt-adducts per nucleotide, which is equivalent to an average of 2 adducts per plasmid. Carboplatin and oxaliplatin show higher efficiencies than cisplatin in the radiosensitization of DNA. Because carboplatin and cisplatin give rise to identical reactive species that attach to DNA, carboplatin must be considered as a better radiosensitizer for equal numbers of Pt-adducts. Conclusion: Platinum chemotherapeutic drugs preferentially enhance the formation of cluster damage to DNA induced by the direct effect of ionizing radiation, and LEEs are the main species responsible for such an enhancement via the formation of electron resonances.« less

New insights into the mechanism underlying the synergistic action of ionizing radiation with platinum chemotherapeutic drugs: the role of low-energy electrons.

PubMed

Rezaee, Mohammad; Hunting, Darel John; Sanche, Léon

2013-11-15

To investigate the efficiencies of platinum chemotherapeutic drugs (Pt-drugs) in the sensitization of DNA to the direct effects of ionizing radiation and to determine the role of low-energy electrons (LEEs) in this process. Complexes of supercoiled plasmid DNA covalently bound to either cisplatin, carboplatin, or oxaliplatin were prepared in different molar ratios. Solid films of DNA and DNA modified by Pt-drugs were irradiated with either 10-KeV or 10-eV electrons. Damages to DNA were quantified by gel electrophoresis, and the yields for damage formation were obtained from exposure-response curves. The presence of an average of 2 Pt-drug-DNA adducts (Pt-adducts) in 3199-bp plasmid DNA increases the probability of a double-strand break by factors of 3.1, 2.5, and 2.4 for carboplatin, cisplatin, and oxaliplatin, respectively. Electrons with energies of 10 eV and 10 KeV interact with Pt-adducts to preferentially enhance the formation of cluster lesions. The maximum increase in radiosensitivity per Pt-adduct is found at ratios up to 3.1×10(-4) Pt-adducts per nucleotide, which is equivalent to an average of 2 adducts per plasmid. Carboplatin and oxaliplatin show higher efficiencies than cisplatin in the radiosensitization of DNA. Because carboplatin and cisplatin give rise to identical reactive species that attach to DNA, carboplatin must be considered as a better radiosensitizer for equal numbers of Pt-adducts. Platinum chemotherapeutic drugs preferentially enhance the formation of cluster damage to DNA induced by the direct effect of ionizing radiation, and LEEs are the main species responsible for such an enhancement via the formation of electron resonances. Copyright © 2013 Elsevier Inc. All rights reserved.

New Insights into the Mechanism Underlying the Synergistic Action of Ionizing Radiation with Platinum Chemotherapeutic Drugs: The Role of Low-Energy Electrons

PubMed Central

Rezaee, Mohammad; Hunting, Darel John; Sanche, Léon

2013-01-01

Purpose To investigate the efficiencies of platinum chemotherapeutic drugs (Pt-drugs) in the sensitization of DNA to the direct effects of ionizing radiation and to determine the role of low-energy electrons (LEEs) in this process. Methods and Materials Complexes of supercoiled plasmid DNA covalently bound to either cisplatin, carboplatin or oxaliplatin were prepared in different molar ratios. Solid films of DNA and DNA modified by Pt-drugs were irradiated with either 10-KeV or 10-eV electrons. DNA damages were quantified by gel electrophoresis, and the yields for damage formation were obtained from exposure-response curves. Results The presence of an average of two Pt-adducts in 3199-bp plasmid DNA increases the probability of a double-strand break by factors of 3.1, 2.5 and 2.4 for carboplatin, cisplatin and oxaliplatin, respectively. Electrons with energies of 10-eV and 10-KeV interact with Pt-adducts to preferentially enhance the formation of cluster lesions. The maximum increase in radiosensitivity per Pt-adduct is found at ratios up to 3.1 × 10−4 Pt-adducts per nucleotide which is equivalent to an average of two adducts per plasmid. Carboplatin and oxaliplatin show higher efficiencies than cisplatin in the radiosensitization of DNA. Since carboplatin and cisplatin give rise to identical reactive species which attach to DNA, carboplatin must be considered as a better radiosensitizers for equal number of Pt-adducts. Conclusion Pt-drugs preferentially enhance the formation of cluster damage to DNA induced by the direct effect of ionizing radiation and LEEs are the main species responsible for such an enhancement via the formation of electron resonances. PMID:23910707

UV-visible-NIR light generation through frequency upconversion in Tm3+-doped low silica calcium aluminosilicate glasses using multiple excitation around 1.2 μm

NASA Astrophysics Data System (ADS)

Trindade, C. M.; Rego-Filho, F. G.; Astrath, N. G. C.; Jacinto, C.; Gouveia-Neto, A. S.

2018-04-01

Intense ultraviolet upconversion emission was produced in single Tm3+-doped OH--free low silica calcium aluminosilicate glasses. A new excitation route based upon multi-Stokes Raman emissions generated in an optical fiber pumped at 1.064 μm, and exploiting the absorption band around 1.2 μm by means of the 3H5 thulium excited state, was used. Furthermore, the other bands of the stimulated Raman scattering spectrum resonantly enhances all the upconversion processes, resulting in efficient ultraviolet (295 nm, 360 nm), blue (456 nm, 480 nm), red (650 nm, 667 nm), and near-infrared (800 nm) emissions. The population of the 1P0, 1D2, 1G4, 3F2 and 3H4 excited-state emitting levels was accomplished through stepwise multi-photon absorption. Results indicate competing cross-relaxation processes involving Tm3+ ion-pairs producing UV emission population quenching Simplified energy-level diagram of Tm3+- doped sample excited using multi-stokes emissions. The λp indication describes all excitation wavelengths, represented by a single arrow for the sake of simplicity.

Three-Photon Luminescence of Gold Nanorods Excited by 1040 nm Femtosecond Laser for High Contrast Tissue and In Vivo Imaging

NASA Astrophysics Data System (ADS)

Wang, Shaowei; Zhao, Xinyuan; Zhang, Hequn; Cai, Fuhong; Qian, Jun

2016-01-01

Gold Nanorods (GNRs) with tunable aspect ratios can strongly absorb and scatter light in the NIR region due to their localized surface plasmon resonance (LSPR) property, and have been demonstrated to exhibit strong plasmon enhanced multiphoton luminescence (MPL) with brightness many times stronger than the conventional organic chromophores. In this study, we synthesized GNRs with longitudinal LSPR peak at 1036 nm to match our home-built light source 1040 nm femtosecond laser, which locates in the “optical window” where the tissue absorbs relatively little light. PEGylated GNRs with great biocompatibility were intravenously injected through the tail vein into mice. Excited by 1040 nm laser, the GNRs exhibit bright three-photon luminescence (3PL) signals while circulating in the blood vessels. The use of GNRs as bright contrast agents for 3PL imaging of mouse ear blood vessels in vivo was demonstrated. And GNRs targeted in tissues can be excited by 1040 nm laser and could be clearly visualized with no autofluorescence background. These results indicated that 3PL of GNRs is very promising for deep in vivo bioimaging and assessing the distribution of GNRs in tissues with high contrast.

Pure single-photon emission from In(Ga)As QDs in a tunable fiber-based external mirror microcavity

NASA Astrophysics Data System (ADS)

Herzog, T.; Sartison, M.; Kolatschek, S.; Hepp, S.; Bommer, A.; Pauly, C.; Mücklich, F.; Becher, C.; Jetter, M.; Portalupi, S. L.; Michler, P.

2018-07-01

Cavity quantum electrodynamics is widely used in many solid-state systems for improving quantum emitter performances or accessing specific physical regimes. For these purposes it is fundamental that the non-classical emitter, like a quantum dot or an NV center, matches the cavity mode, both spatially and spectrally. In the present work, we couple single photons stemming from In(Ga)As quantum dots into an open fiber-based Fabry–Pérot cavity. Such a system allows for reaching an optimal spatial and spectral matching for every present emitter and every optical transition, by precisely tuning the cavity geometry. In addition to that, the capability of deterministically and repeatedly locating a single quantum dot enables to compare the behavior of the quantum emitter inside the cavity with respect to before it is placed inside. The presented open-cavity system shows full flexibility by precisely tuning in resonance different QD transitions, namely excitons, biexcitons and trions. A measured Purcell enhancement of 4.4 ± 0.5 is obtained with a cavity finesse of about 140, while still demonstrating a single-photon source with vanishing multi-photon emission probability.

Rotationally inelastic scattering of ND3 with H2 as a probe of the intermolecular potential energy surface

NASA Astrophysics Data System (ADS)

Tkáč, Ondřej; Saha, Ashim K.; Loreau, Jérôme; Ma, Qianli; Dagdigian, Paul J.; Parker, David H.; van der Avoird, Ad; Orr-Ewing, Andrew J.

2015-12-01

Differential cross sections (DCSs) are reported for rotationally inelastic scattering of ND3 with H2, measured using a crossed molecular beam apparatus with velocity map imaging (VMI). ND3 molecules were quantum-state selected in the ground electronic and vibrational levels and, optionally, in the j±k = 11- rotation-inversion level prior to collisions. Inelastic scattering of state-selected ND3 with H2 was measured at the mean collision energy of 580 cm-1 by resonance-enhanced multiphoton ionisation spectroscopy and VMI of ND3 in selected single final j'±k' levels. Comparison of experimental DCSs with close-coupling quantum-mechanical scattering calculations serves as a test of a recently reported ab initio potential energy surface. Calculated integral cross sections reveal the propensities for scattering into various final j'±k' levels of ND3 and differences between scattering by ortho and para H2. Integral and differential cross sections are also computed at a mean collision energy of 430 cm-1 and compared to our recent results for inelastic scattering of state-selected ND3 with He.

Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability

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

Isselhardt, Brett H.

2011-09-01

Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of 235U/ 238U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser inmore » a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.« less

Temperature dependence of the photodissociation of CO2 from high vibrational levels: 205-230 nm imaging studies of CO(X1Σ+) and O(3P, 1D) products

NASA Astrophysics Data System (ADS)

Sutradhar, S.; Samanta, B. R.; Samanta, A. K.; Reisler, H.

2017-07-01

The 205-230 nm photodissociation of vibrationally excited CO2 at temperatures up to 1800 K was studied using Resonance Enhanced Multiphoton Ionization (REMPI) and time-sliced Velocity Map Imaging (VMI). CO2 molecules seeded in He were heated in an SiC tube attached to a pulsed valve and supersonically expanded to create a molecular beam of rotationally cooled but vibrationally hot CO2. Photodissociation was observed from vibrationally excited CO2 with internal energies up to about 20 000 cm-1, and CO(X1Σ+), O(3P), and O(1D) products were detected by REMPI. The large enhancement in the absorption cross section with increasing CO2 vibrational excitation made this investigation feasible. The internal energies of heated CO2 molecules that absorbed 230 nm radiation were estimated from the kinetic energy release (KER) distributions of CO(X1Σ+) products in v″ = 0. At 230 nm, CO2 needs to have at least 4000 cm-1 of rovibrational energy to absorb the UV radiation and produce CO(X1Σ+) + O(3P). CO2 internal energies in excess of 16 000 cm-1 were confirmed by observing O(1D) products. It is likely that initial absorption from levels with high bending excitation accesses both the A1B2 and B1A2 states, explaining the nearly isotropic angular distributions of the products. CO(X1Σ+) product internal energies were estimated from REMPI spectroscopy, and the KER distributions of the CO(X1Σ+), O(3P), and O(1D) products were obtained by VMI. The CO product internal energy distributions change with increasing CO2 temperature, suggesting that more than one dynamical pathway is involved when the internal energy of CO2 (and the corresponding available energy) increases. The KER distributions of O(1D) and O(3P) show broad internal energy distributions in the CO(X1Σ+) cofragment, extending up to the maximum allowed by energy but peaking at low KER values. Although not all the observations can be explained at this time, with the aid of available theoretical studies of CO2 VUV photodissociation and O + CO recombination, it is proposed that following UV absorption, the two lowest lying triplet states, a3B2 and b3A2, and the ground electronic state are involved in the dynamical pathways that lead to product formation.

Spectral phase measurement of a Fano resonance using tunable attosecond pulses

PubMed Central

Kotur, M.; Guénot, D.; Jiménez-Galán, Á; Kroon, D.; Larsen, E. W.; Louisy, M.; Bengtsson, S.; Miranda, M.; Mauritsson, J.; Arnold, C. L.; Canton, S. E.; Gisselbrecht, M.; Carette, T.; Dahlström, J. M.; Lindroth, E.; Maquet, A.; Argenti, L.; Martín, F.; L'Huillier, A.

2016-01-01

Electron dynamics induced by resonant absorption of light is of fundamental importance in nature and has been the subject of countless studies in many scientific areas. Above the ionization threshold of atomic or molecular systems, the presence of discrete states leads to autoionization, which is an interference between two quantum paths: direct ionization and excitation of the discrete state coupled to the continuum. Traditionally studied with synchrotron radiation, the probability for autoionization exhibits a universal Fano intensity profile as a function of excitation energy. However, without additional phase information, the full temporal dynamics cannot be recovered. Here we use tunable attosecond pulses combined with weak infrared radiation in an interferometric setup to measure not only the intensity but also the phase variation of the photoionization amplitude across an autoionization resonance in argon. The phase variation can be used as a fingerprint of the interactions between the discrete state and the ionization continua, indicating a new route towards monitoring electron correlations in time. PMID:26887682

Diode laser based resonance ionization mass spectrometric measurement of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1997-10-01

A diode laser based scheme for the isotopically selective excitation and ionization of strontium is presented. The double-resonance excitation 5s 21S 0→5s5p 3P 1→5s6s 3S 1 is followed by photoionization at 488 nm. The isotope shifts and hyperfine structure in the resonance transitions have been accurately measured for the stable isotopes and 90Sr, with the measurement of the 90Sr shifts using sub-pg samples. Analytical tests, using graphite crucible atomization, demonstrated 90Sr detection limits of 0.8 fg and overall (optical+mass spectrometer) isotopic selectivity of >10 10 against stable strontium.

Efficient and robust photo-ionization loading of beryllium ions

NASA Astrophysics Data System (ADS)

Wolf, Sebastian; Studer, Dominik; Wendt, Klaus; Schmidt-Kaler, Ferdinand

2018-02-01

We demonstrate the efficient generation of Be^+ ions with a 60 ns and 150 nJ laser pulse near 235 nm for two-step photo-ionization, proven by subsequent counting of the number of ions loaded into a linear Paul trap. The bandwidth and power of the laser pulse are chosen in such a way that a first, resonant step fully saturates the entire velocity distribution of beryllium atoms effusing from a thermal oven. The second excitation step is driven by the same light field causing efficient non-resonant ionization. Our ion-loading scheme has a similar efficiency as compared to former pathways using two-photon continuous wave laser excitation, but with an order of magnitude lower than average UV light power.

Laser machining of explosives

DOEpatents

Perry, Michael D.; Stuart, Brent C.; Banks, Paul S.; Myers, Booth R.; Sefcik, Joseph A.

2000-01-01

The invention consists of a method for machining (cutting, drilling, sculpting) of explosives (e.g., TNT, TATB, PETN, RDX, etc.). By using pulses of a duration in the range of 5 femtoseconds to 50 picoseconds, extremely precise and rapid machining can be achieved with essentially no heat or shock affected zone. In this method, material is removed by a nonthermal mechanism. A combination of multiphoton and collisional ionization creates a critical density plasma in a time scale much shorter than electron kinetic energy is transferred to the lattice. The resulting plasma is far from thermal equilibrium. The material is in essence converted from its initial solid-state directly into a fully ionized plasma on a time scale too short for thermal equilibrium to be established with the lattice. As a result, there is negligible heat conduction beyond the region removed resulting in negligible thermal stress or shock to the material beyond a few microns from the laser machined surface. Hydrodynamic expansion of the plasma eliminates the need for any ancillary techniques to remove material and produces extremely high quality machined surfaces. There is no detonation or deflagration of the explosive in the process and the material which is removed is rendered inert.

Overcritical plasma ignition and diagnostics from oncoming interaction of two color low energy tightly focused femtosecond laser pulses inside fused silica

NASA Astrophysics Data System (ADS)

Potemkin, F. V.; Bravy, B. G.; Bezsudnova, Yu I.; Mareev, E. I.; Starostin, V. M.; Platonenko, V. T.; Gordienko, V. M.

2016-04-01

We report overcritical (3.3  ×  1021 cm-3) microplasma produced by low energy colliding IR (infrared) (1.24 μm) and visible (0.62 μm) femtosecond pulses tightly focused (NA  =  0.5) into the bulk of fused silica with on-line monitoring based on third harmonic generated by the IR beam. It was established that the absorbed energy density is the key parameter that determines the micromodification formation threshold and in our experimental conditions it is close to 4.5 kJ cm-3. Non-monotonic behavior of the third harmonic signal as a function of time delay between visible (0.62 μm) and IR (1.24 μm) femtosecond pulses demonstrates the qualitative differences about the two phenomena: one is the seed electrons generation by the visible pulse via multiphoton ionization and second is the avalanche ionization by the IR pulse. We predict that the tandem two-color excitation of wide-bandgap dielectric in comparison with single-color pulse interaction regime allows providing a much higher absorbed energy density and overcritical plasma.

Combination of electrospray ionization, atmospheric pressure photoionization and laser desorption ionization Fourier transform ion cyclotronic resonance mass spectrometry for the investigation of complex mixtures - Application to the petroleomic analysis of bio-oils.

PubMed

Hertzog, Jasmine; Carré, Vincent; Le Brech, Yann; Mackay, Colin Logan; Dufour, Anthony; Mašek, Ondřej; Aubriet, Frédéric

2017-05-29

The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to C x H y O z with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparing Laser Desorption Ionization and Atmospheric Pressure Photoionization Coupled to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry To Characterize Shale Oils at the Molecular Level

USGS Publications Warehouse

Cho, Yunjo; Jin, Jang Mi; Witt, Matthias; Birdwell, Justin E.; Na, Jeong-Geol; Roh, Nam-Sun; Kim, Sunghwan

2013-01-01

Laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze shale oils. Previous work showed that LDI is a sensitive ionization technique for assessing aromatic nitrogen compounds, and oils generated from Green River Formation oil shales are well-documented as being rich in nitrogen. The data presented here demonstrate that LDI is effective in ionizing high-double-bond-equivalent (DBE) compounds and, therefore, is a suitable method for characterizing compounds with condensed structures. Additionally, LDI generates radical cations and protonated ions concurrently, the distribution of which depends upon the molecular structures and elemental compositions, and the basicity of compounds is closely related to the generation of protonated ions. This study demonstrates that LDI FT-ICR MS is an effective ionization technique for use in the study of shale oils at the molecular level. To the best of our knowledge, this is the first time that LDI FT-ICR MS has been applied to shale oils.

Modeling of Nonlinear Optical Response in Gaseous Media and Its Comparison with Experiment

NASA Astrophysics Data System (ADS)

Xia, Yi

This thesis demonstrates the model and application of nonlinear optical response with Metastable Electronic State Approach (MESA) in ultrashort laser propagation and verifies accuracy of MESA through extensive comparison with experimental data. The MESA is developed from quantum mechanics to describe the nonlinear off-resonant optical response together with strong-field ionization in gaseous medium. The conventional light-matter interaction models are based on a piece-wise approach where Kerr effect and multi-photon ionization are treated as independent nonlinear responses. In contrast, MESA is self-consistent as the response from freed electrons and bound electrons are microscopically linked. It also can be easily coupled to the Unidirectional Pulse Propagation Equations (UPPE) for large scale simulation of experiments. This work tests the implementation of MESA model in simulation of nonlinear phase transients of ultrashort pulse propagation in a gaseous medium. The phase transient has been measured through Single-Shot Supercontinuum Spectral Interferometry. This technique can achieve high temporal resolution (10 fs) and spatial resolution (5 mum). Our comparison between simulation and experiment gives a quantitive test of MESA model including post-adiabatic corrections. This is the first time such a comparison was achieved for a theory suitable for large scale numerical simulation of modern nonlinear-optics experiments. In more than one respect, ours is a first-of-a-kind achievement. In particular, • Large amount of data are compared. We compare the data of nonlinear response induced by different pump intensity in Ar and Nitrogen. The data sets are three dimensions including two transverse spacial dimensions and one axial temporal dimension which reflect the whole structure of nonlinear response including the interplay between Kerr and plasma-induced effects. The resolutions of spatial and temporal dimension are about a few micrometer and several femtosecond. • The regime of light-matter interaction investigated here is between the strong and perturbative, where the pulse intensity can induce nonlinear refractive index change and partial ionization of dielectric medium. Obviously, such regimes are difficult to study both experimentally and theoretically. • MESA is a quantum based model, but it retains the same computation complexity as conventional light-matter interaction model. MESA contains the response from both bound and continuum states in a single self-consistent "Package". So, it is fair to say that this experiment-theory comparison sets a new standard for nonlinear light-matter interaction models and their verification in the area of extreme nonlinear optics.