Field-induced Ionization Research Articles

Coherent control of interaction and entanglement of a Rydberg atom with few photons

The interaction of a model Rydberg atom with a single photon quantum field is investigated. The atom is considered in the model of ‘several bound states+continuum’, so that the field-induced ionization from initially populated Rydberg states as well as the resonance coupling with a lower-lying bound state are taken into account. The significant suppression of the ionization due to interference mechanism is established and strong entanglement with a quantum field subsystem is found. Methods to control the atomic behavior and to produce strongly entangled atom–photon states are suggested. The possibility to measure the degree of entanglement experimentally is demonstrated.

Activationless charge transport across 4.5 to 22 nm in molecular electronic junctions

In this work, we bridge the gap between short-range tunneling in molecular junctions and activated hopping in bulk organic films, and greatly extend the distance range of charge transport in molecular electronic devices. Three distinct transport mechanisms were observed for 4.5-22-nm-thick oligo(thiophene) layers between carbon contacts, with tunneling operative when d < 8 nm, activated hopping when d > 16 nm for high temperatures and low bias, and a third mechanism consistent with field-induced ionization of highest occupied molecular orbitals or interface states to generate charge carriers when d = 8-22 nm. Transport in the 8-22-nm range is weakly temperature dependent, with a field-dependent activation barrier that becomes negligible at moderate bias. We thus report here a unique, activationless transport mechanism, operative over 8-22-nm distances without involving hopping, which severely limits carrier mobility and device lifetime in organic semiconductors. Charge transport in molecular electronic junctions can thus be effective for transport distances significantly greater than the 1-5 nm associated with quantum-mechanical tunneling.

Investigation on the Role of Pneumatic Aspects in Electrospray, Desorption Electrospray Surface Ionization and Surface-Activated Chemical Ionization

This review reports the results of some studies carried out by us on the role of pneumatic aspects in electrospray and desorption electrospray surface ionization, with the aim to propose some relevant aspects of the mechanisms involved in these ionization methods. Electrospray ion sources, with the exception of the nano- electrospray source, operate with the concurrent action of a strong electrical field and a supplementary coaxial gas flow. The electrical field is responsible for electrospraying of the analyte solution but the use of a coaxial gas flow leads to a significant increase of the analyte signal and allows the use of higher solution flows. However, by employing capillary voltages much lower than those necessary to activate the electrospray phenomenon, analyte ions are still observed and this indicates that different mechanisms must be operative for ion production. Under these conditions, ion generation could take place from the neutral pneumatically sprayed droplet by field-induced droplet ionization. Also in the case of desorption electrospray ionization (DESI), and without any voltage on the spraying capillary as well as on the surface of interest, ions of analytes present on the surface become detectable and this shows that desorption/ionization of analytes occurs by neutral droplets impinging the surface. Consequently, the pneumatic effect of the impinging droplets plays a relevant role, and for these reasons the method has been called pneumatic assisted desorption (PAD). Some analogies existing between PAD and surface activated chemical ionization (SACI), based on the insertion of a metallic surface inside an atmospheric pressure chemical ionization source operating without corona discharge, are discussed.

Studying Interfacial Reactions of Cholesterol Sulfate in an Unsaturated Phosphatidylglycerol Layer with Ozone Using Field Induced Droplet Ionization Mass Spectrometry

Field-induced droplet ionization (FIDI) is a recently developed ionization technique that can transfer ions from the surface of microliter droplets to the gas phase intact. The air-liquid interfacial reactions of cholesterol sulfate (CholSO(4)) in a 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) surfactant layer with ozone (O(3)) are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Time-resolved studies of interfacial ozonolysis of CholSO(4) reveal that water plays an important role in forming oxygenated products. An epoxide derivative is observed as a major product of CholSO(4) oxidation in the FIDI-MS spectrum after exposure of the droplet to O(3) for 5 s. The abundance of the epoxide product then decreases with continued O(3) exposure as the finite number of water molecules at the air-liquid interface becomes exhausted. Competitive oxidation of CholSO(4) and POPG is observed when they are present together in a lipid surfactant layer at the air-liquid interface. Competitive reactions of CholSO(4) and POPG with O(3) suggest that CholSO(4) is present with POPG as a well-mixed interfacial layer. Compared with CholSO(4) and POPG alone, the overall ozonolysis rates of both CholSO(4) and POPG are reduced in a mixed layer, suggesting the double bonds of both molecules are shielded by additional hydrocarbons from one another. Molecular dynamics simulations of a monolayer comprising POPG and CholSO(4) correlate well with experimental observations and provide a detailed picture of the interactions between CholSO(4), lipids, and water molecules in the interfacial region.

Phase dependence of electron localization in HeH^2+ dissociation with an intense few-cycle laser pulse

The electron localization in the dissociation of the asymmetric charged molecular ion HeH$^{2+}$ exposed to an intense few-cycle laser pulse is studied by solving numerically the 3D time-dependent Schr\"odinger equation. By varying the carrier-envelope phase (CEP) and the intensity of the pulse, the upward shift of the localization probability and the suppression of the dissociation channel He$^{2+}$+H are observed . Our analysis shows that the phenomenon is attributed to the asymmetric structure of the molecule as well as the recollision-assistant field-induced ionization of the electron wave packets localized on H$^+$ in the trailing of the pulse.

Effect of a transverse magnetic field on the plume emission in laser-produced plasma: An atomic analysis

We have investigated the effect of varying transverse magnetic field on the plasma plume emission of laser-produced lithium plasma. Two atomic transitions for lithium neutral Li (I) and two for Li ion LI (II) are taken for the study. It has been found that for Li (I), the emission from 670.8 nm transition (2s 2S 1/2←2p 2P 3/2 ′ 1/2) shows initial enhancement and then subsequent decrease for higher fields. Of course, the overall intensity is increased for all the fields when compared to the case of without field. On the other hand, for 610.3 nm (2p 2P 1/2←3d 2P 3/2 ′ 5/2), there is continuous decrease in intensity. Interestingly, for Li (II) transitions also, after an initial increase in intensity up to 0.08 Ta decrease is observed. From the atomic analysis, we find that for 670.8 nm line, the cause of initial enhancement is increase in electron impact excitation whereas for decreased intensity, increased field-induced ionization appears to be responsible mechanism. However, for 610.3 nm line, decrease in intensity appears to be due to decreased recombination. For Li (II), 478.8 nm (3p 1P 1←4d 1D 2) and 548.4 nm (2s 3S 1←2p 3P 2,1,0) transitions, initial increase appears to be due to increased confinement (increase in plasma density) and subsequent decrease in intensity with increase in field due to decreased recombination.

Interfacial reactions of ozone with surfactant protein B in a model lung surfactant system.

Oxidative stresses from irritants such as hydrogen peroxide and ozone (O(3)) can cause dysfunction of the pulmonary surfactant (PS) layer in the human lung, resulting in chronic diseases of the respiratory tract. For identification of structural changes of pulmonary surfactant protein B (SP-B) due to the heterogeneous reaction with O(3), field-induced droplet ionization (FIDI) mass spectrometry has been utilized. FIDI is a soft ionization method in which ions are extracted from the surface of microliter-volume droplets. We report structurally specific oxidative changes of SP-B(1-25) (a shortened version of human SP-B) at the air-liquid interface. We also present studies of the interfacial oxidation of SP-B(1-25) in a nonionizable 1-palmitoyl-2-oleoyl-sn-glycerol (POG) surfactant layer as a model PS system, where competitive oxidation of the two components is observed. Our results indicate that the heterogeneous reaction of SP-B(1-25) at the interface is quite different from that in the solution phase. In comparison with the nearly complete homogeneous oxidation of SP-B(1-25), only a subset of the amino acids known to react with ozone are oxidized by direct ozonolysis in the hydrophobic interfacial environment, both with and without the lipid surfactant layer. Combining these experimental observations with the results of molecular dynamics simulations provides an improved understanding of the interfacial structure and chemistry of a model lung surfactant system subjected to oxidative stress.

Evaporation and Discharge Dynamics of Highly Charged Multicomponent Droplets Generated by Electrospray Ionization

We investigate the Rayleigh discharge and evaporation dynamics of highly charged two-component droplets consisting principally of methanol with 2-methoxyethanol, tert-butanol, or m-nitrobenzyl alcohol. A phase Doppler anemometer (PDA) characterizes droplets generated by electrospray ionization (ESI) according to size, velocity, and charge as they move through a uniform electric field within an ion mobility spectrometer (IMS). Repeated field reversals result in droplet "ping-pong" through the PDA. This generates individual droplet histories of solvent evaporation behavior and the dynamics of charge loss to progeny droplets during Rayleigh discharge events. On average, methanol droplets discharge at 127% their Rayleigh limit of charge, q(R), and release 25% of the net charge. Charge loss from methanol/2-methoxyethanol droplets behaves similarly to pure 2-methoxyethanol droplets which release approximately 28% of their net charge. Binary methanol droplets containing up to 50% tert-butanol discharge at a lower percent q(R) than pure methanol and release a greater fraction of their net charge. Mixed 99% methanol/1% m-nitrobenzyl alcohol droplets possess discharge characteristics similar to those of methanol. However, droplets of methanol containing 2% m-nitrobenzyl evaporate down to a fixed size and charge that remains constant with no observable discharges. Quasi-steady-state evaporation models accurately describe observed evaporation phenomena in which methanol/tert-butanol droplets evaporate at a rate similar to that of pure methanol and methanol/2-methoxyethanol droplets evaporate at a rate similar to that of 2-methoxyethanol. We compare these results to previous Rayleigh discharge experiments and discuss the implications for binary solvents in electrospray mass spectrometry (ESI-MS) and field-induced droplet ionization mass spectrometry (FIDI-MS).

Excitonic optical absorption in semiconductors under intense terahertz radiation

The excitonic optical absorption of GaAs bulk semiconductors under intense terahertz (THz) radiation is investigated numerically. The method of solving initial-value problems, combined with the perfect matched layer technique, is used to calculate the optical susceptibility. In the presence of a driving THz field, in addition to the usual exciton peaks, 2p replica of the dark 2p exciton and even-THz-photon-sidebands of the main exciton resonance emerge in the continuum above the band edge and below the main exciton resonance. Moreover, to understand the shift of the position of the main exciton peak under intense THz radiation, it is necessary to take into consideration both the dynamical Franz–Keldysh effect and ac Stark effect simultaneously. For moderate frequency fields, the main exciton peak decreases and broadens due to the field-induced ionization of the excitons with THz field increasing. However, for high frequency THz fields, the characteristics of the exciton recur even under very strong THz fields, which accords with the recent experimental results qualitatively.

Detection of field-induced single-acceptor ionization in Si by single-hole-tunneling transistor

The authors have detected the ionization of single-acceptors in the underlying p on p+ substrate of a silicon-on-insulator (SOI) wafer using a single-hole-tunneling (SHT) transistor fabricated in the top Si layer of the SOI at low temperatures. It was found that freeze-out boron atoms in the substrate are sequentially ionized from near the buried SiO2∕p-Si substrate interface to deeper positions by application of a vertical electric field, creating steplike features in the time-dependent SHT current.

Ultrafast Electronuclear Dynamics ofH2Double Ionization

The ultrafast electronic and nuclear dynamics of H2 laser-induced double ionization is studied using a time-dependent wave packet approach that goes beyond the fixed nuclei approximation. The double ionization pathways are analyzed by following the evolution of the total wave function during and after the pulse. The rescattering of the first ionized electron produces a coherent superposition of excited molecular states which presents a pronounced transient H+H- character. This attosecond excitation is followed by field-induced double ionization and by the formation of short-lived autoionizing states which decay via double ionization. These two double ionization mechanisms may be identified by their signature imprinted in the kinetic-energy distribution of the ejected protons.

Electron-diffraction imaging of nuclear dynamics in molecules

We investigate the formation of the diffraction image of a molecule arising in the rescattering process during field-induced molecular ionization. The problem is solved numerically by integration of the non-stationary two-electron Schrödinger equation. The observed diffraction patterns are used to extract the information about molecular orientation and internuclear separation. The validity of a simple double slit diffraction rule is examined, and additional phase corrections are obtained to provide high accuracy. The role of the presence of the bound electron in the parent molecular ion in the scattering process is analysed.

Probing Interfacial Chemistry of Single Droplets with Field-Induced Droplet Ionization Mass Spectrometry: Physical Adsorption of Polycyclic Aromatic Hydrocarbons and Ozonolysis of Oleic Acid and Related Compounds

The recently developed technique of field-induced droplet ionization (FIDI) is applied to study interfacial chemistry of a single droplet. In a new variation of the FIDI method, 1-2-mm-diameter droplets hang from a capillary and undergo heterogeneous reactions between solution-phase analytes and gas-phase species. Following a specified reaction time, the application of a high electric field induces FIDI in the droplet, generating fine jets of highly charged progeny droplets that are characterized by mass spectrometry. Sampling over a range of delay times following exposure of the droplet to gas-phase reactants, the spectra yield the temporal variation of reactant and product concentrations. We illustrate the technique with three examples: the adsorption of the polycyclic aromatic hydrocarbon naphthalene into a water-methanol droplet, the ozonolysis of oleic acid, and localization of the carbon-carbon double bond within a lysophosphatidic acid. Gas-phase naphthalene reacts with 80% methanol-20% water droplets containing 100 microM silver nitrate. Positive ion mass spectra show increasing concentrations of silver ion-naphthalene adducts as exposure times increase. To examine the ozonolysis of organic molecules, gas-phase ozone generated by a mercury pencil-style lamp reacts with either 10 microM oleic acid or 100 microM oleoyl-L-alpha-lysophosphatidic acid (LPA; 18:1). Negative ion spectra from the ozonolysis of oleic acid show azelaic acid and 9-oxononanoic acid as the principle reaction products. Ozonolysis products from LPA (18:1) unambiguously demonstrate the double bond position in the original phospholipid.

Dynamics of Field-Induced Droplet Ionization: Time-Resolved Studies of Distortion, Jetting, and Progeny Formation from Charged and Neutral Methanol Droplets Exposed to Strong Electric Fields

We recently reported that strong electric fields may be employed to directly extract positive and negative ions for mass analysis, including intact proteins, from neutral droplets. The present study investigates the dynamics of this process using switched high electric fields to enable time-resolved studies of droplet distortion, Taylor cone formation, and charged progeny droplet extraction from neutral and charged 225 microm methanol droplets. After a specific time in the field, a flashlamp is triggered to record droplet distortions using shadow photography. At a critical field strength E(c)0 corresponding to the Taylor limit, neutral droplets exhibit a prolate elongation along the field axis forming symmetric cone-jets of positive and negatively charged progeny droplets, approximately 10 microm in diameter. This process is termed field-induced droplet ionization (FIDI). Because the time scale of FIDI is related to the frequency of shape oscillations that occur below the Taylor limit, models of field-dependent oscillation become an important predictor of the time scale for progeny jet formation. Droplets with a net charge q distort into asymmetric tear shapes and emit a single charged jet of progeny at a critical field E(c)(q) that is less than E(c)0. The measured decrease in droplet stream charge indicates that total charge loss can be greater than the original charge on the droplet, resulting in oppositely charged droplets. Interestingly, above E(c)0, charged droplets sequentially emit a jet of the same polarity as the net charge followed by a jet of reverse polarity emitted in the opposite direction. For both neutral and charged droplets, increasing the electric field decreases the time to form jets and the combination of net charge and higher-than-critical fields has a compound effect in accelerating progeny formation. The implications of our results for using switched fields in FIDI-mass spectrometry for on-demand ion sampling from neutral and charged droplets are discussed.

Effects of confinement on the Rydberg molecule NeH

Ab initio potential energy curves of the Rydberg NeH molecule in the presence of cylindrical spatial confinement were computed by the method of multi-reference configuration interaction with extended basis sets. The influence of the applied potential to the structures and spectra of the ground and excited states of NeH was analysed in terms of perturbation theory. In addition, the phenomenon of field-induced ionization was discussed.

Coulomb explosion of propane in intense femtosecond laser fields

Femtosecond laser-induced Coulomb explosion of C3H8 is investigated experimentally by means of time-of-flight mass spectrometry at different intensities. The mass spectrum of C3H8 presents much more abundant fragments than obtained through electron-impact ionization. The appearance of intermediate daughter molecular ions with a double-peak structure shows that Coulomb explosion of C3H8 undergoes a two-step process. One C–C bond of the C3 carbon skeleton breaks first and then the other C–C bond breaks. The ion yields and initial kinetic energy releases of ionic fragments increase with increasing laser intensity. The C2+ and H+2 ions exhibit anisotropic angular distributions, with a maximum along the laser polarization vector and a minimum perpendicular to it. The geometric alignment is the main reason for the measured anisotropic angular distributions of ionic fragments. A significant decrease of ionization occurs in circular polarization and elliptical polarization. This fact reveals that field-induced ionization is responsible for the formation mechanism of molecular ions.

Dissociative ionization of methane by chirped pulses of intense laser light.

Measurements have been made of optical field-induced ionization and fragmentation of methane molecules at laser intensities in the 10(16) W cm(-2) range using near transform limited pulses of 100 fs duration as well as with chirped pulses whose temporal profiles extend up to 1500 fs. Data is taken both in constant-intensity and constant-energy modes. The temporal profile of the chirped laser pulse is found to affect the morphology of the fragmentation pattern that is measured. Besides, the sign of the chirp also affects the yield of fragments like C2+, H+, and H2+ that originate from methane dications that are formed by optical field-induced double ionization.

Field-Induced Droplet Ionization Mass Spectrometry

A neutral droplet elongates along the axis of a strong electric field, ejecting opposing jets of positively and negatively charged progeny droplets. Images of droplets from a vibrating orifice aerosol generator illustrate this phenomenon, and mass spectrometric sampling of the progeny droplets demonstrates that they are a viable source of desolvated gas-phase ions. Field-induced droplet ionization (FIDI) mass spectra are presented for several species, including tetraheptylammonium cation, deprotonated benzene tetracarboxylic acid anion, and multiply protonated cytochrome c.

Field-induced ionization and Coulomb explosion of CO 2 by intense femtosecond laser pulses

Field-induced ionization and Coulomb explosion of the triatomic molecule CO 2 were systematically investigated by using a time-of-fight (TOF) mass spectrometer under an intense femtosecond laser field of different polarization with the intensities from 1.0×10 15 W/cm 2 to 1.2×10 16 W/cm 2. The appearances of the highly charged atomic ions and the peak splitting indicate that these atomic ions originate from Coulomb explosion of the highly charged molecular ions. The Coulomb explosion was proved to be a concerted process and two CO bonds broke simultaneously. Compared with the linearly polarized light, suppression of ionization occurs for the elliptically and circularly polarized lights. The angular distributions of the parent molecular ions are all isotropic. The collinear O m+ ( m≤3) and orthogonal C n+ ( n≤3) distributions show that the molecule structure is being distorted and bent by the intense laser field. Analyzing the signal intensities obtained using linearly polarized light and circularly polarized light with equal electric field amplitude, the dynamic alignment mechanism is revealed to be responsible for the anisotropic angular distributions of O m+ ( m≤3) and C n+ ( n≤3) ions.

Particle-in-cell simulations of tunneling ionization effects in plasma-based accelerators

Plasma-based accelerators can sustain accelerating gradients on the order of 100 GV/m. If the plasma is not fully ionized, fields of this magnitude will ionize neutral atoms via electron tunneling, which can completely change the dynamics of the plasma wake. Particle-in-cell simulations of a high-field plasma wakefield accelerator, using the OOPIC code [D. L. Bruhwiler et al., Phys. Rev. ST Accel. Beams 4, 101302 (2001)], which includes field-induced tunneling ionization of neutral Li gas, show that the presence of even moderate neutral gas density significantly degrades the quality of the wakefield. The tunneling ionization model in OOPIC has been validated via a detailed comparison with experimental data from the l’OASIS laboratory [W.P. Leemans et al., Phys. Rev. Lett. 89, 174802 (2002)]. The properties of a wake generated directly from a neutral gas are studied, showing that one can recover the peak fields of the fully ionized plasma simulations, if the density of the electron drive bunch is increased such that the bunch rapidly ionizes the gas.