Field-induced Ionization Research Articles

Transition Metal Ions in Solution: Complexed Ion Speciation at the Air-Liquid Interface.

We have studied the interfacial properties of Zn2+ vs selected transition metal cations such as Fe2+, Cu2+, and Cr3+ in a water-ethanol mixture using field-induced droplet ionization. This was in particular inspired by the specific surface activity of Zn2+ that has been observed on several occasions and a desire to clarify the root cause for this behavior. We have found that Zn2+, due to its unique electronic configuration and atomic size, is the only ion of those under study that gives rise to specific speciation at the air-liquid interface with three ethanol molecules attached to the central atom for optimal polarity.

Electric field induced dissociation of a confined hydrogen molecule

The effect of a static electric field ionization on the neutral hydrogen molecule H2 confined in a spherical potential well is studied, as a simple model for the chemical activation of molecular species in a medium. Quantum diffusion Monte Carlo is employed with complete account of electron correlation. Field-induced ionization and dissociation are discussed, for different values of the confinement radius and electric field strength. This study allows to highlight the mechanism of electric field initiation of chemical reactions in fluids at different pressures, without the details of a specific chemical environment.

Hole transport mechanism at high temperatures in p-GaN/AlGaN/GaN heterostructure

This Letter reports an investigation of hole transport in p-GaN/AlGaN/GaN heterostructures through experimental and theoretical analyses under varied conditions. Highly non-linear current–voltage (I–V) characteristics, obtained via the linear transmission line method measurements, are utilized for this study. At low bias voltage, the transport can be ascribed to the Schottky nature of the contact, while at high bias, the conduction is observed to be governed by space-charge limited current (SCLC). The Schottky characteristics (Schottky barrier height and non-ideality factor) and the SCLC exponent were analyzed for devices with varying contact spacings and at different high temperatures. The SCLC exponent, m, is in the range of 2≤m≤4 depending on the applied voltage range, revealing the existence of the trap states in the channel region. The findings of this work indicate that the charge injection, field-induced ionization, and trap states in the p-GaN channel are critical factors in the current transport of p-GaN/AlGaN/GaN heterostructure.

Tools to Investigate Structure at Hydrocarbon–Air Interfaces: Field-Induced Droplet Ionization Mass Spectrometry and Sum-Frequency Generation with Pulsed Lasers

Tools to Investigate Structure at Hydrocarbon–Air Interfaces: Field-Induced Droplet Ionization Mass Spectrometry and Sum-Frequency Generation with Pulsed Lasers

First passage time of laser-driven tunneling.

The notion of the first passage time is shown to offer a meaningful extension to quantum tunneling, providing a closed-integral-form analytical unification of the tunneling rate and the tunneling passage time. We demonstrate that, in suitable potential settings, the quantum first passage time, found as a solution to the Fokker-Planck and backward Kolmogorov's equations for the quantum probability density, recovers the hallmark results for the Kramers escape rate, the lifetime of tunneling quasi-stationary wave packets, leads to a classical, distance-over-speed passage time for a free-particle wave function, and offers useful insights into Keldysh's intimation on the electron barrier-traversal time in field-induced ionization.

Fast Hydroxyl Radical Generation at the Air-Water Interface of Aerosols Mediated by Water-Soluble PM2.5 under Ultraviolet A Radiation.

Due to the adverse health effects and the role in the formation of secondary organic aerosols, hydroxyl radical (OH) generation by atmospheric fine particulate matter (PM) has been of particular research interest in both bulk solutions and the gas phase. However, OH generation by PM at the air-water interface of atmospheric water droplets, a unique environment where reactions can be accelerated by orders of magnitude, has long been overlooked. Using the field-induced droplet ionization mass spectrometry methodology that selectively samples molecules at the air-water interface, here, we show significant oxidation of amphiphilic lipids and isoprene mediated by water-soluble PM2.5 at the air-water interface under ultraviolet A irradiation, with the OH generation rate estimated to be 1.5 × 1016 molecule·s-1·m-2. Atomistic molecular dynamics simulations support the counter-intuitive affinity for the air-water interface of isoprene. We opine that it is the carboxylic chelators of the surface-active molecules in PM that enrich photocatalytic metals such as iron at the air-water interface and greatly enhance the OH generation therein. This work provides a potential new heterogeneous OH generation channel in the atmosphere.

Mass Spectrometry and Cryogenic Electron Microscopy Illuminate Molecular-Level Mechanisms of the Oxidative and Structural Damage to Lipid Membranes by Radical-Bearing Graphene Oxide.

Biomedical applications of graphene in tumor and bacterial treatment have become cutting-edge fields due to its unique physical and chemical properties. However, a mechanistic understanding of the interactions and reactions between graphene-based material and biological systems such as lipid membranes remains elusive, especially at the molecular level. By using the unique field-induced droplet ionization mass spectrometry and cryogenic electron microscopy methodologies, we reveal the oxidation products of monolayer lipid membranes at the air-water interface and the change in the morphology of bilayer lipid membranes in an aqueous solution caused by the incorporation of graphene oxide bearing π-conjugated carbon radicals [hydrated graphene oxide (hGO)]. We discovered that hGO is an efficient source of hydroxyl radicals and that it is not only the incorporation of the hGO sheets but also the irregular packing of the lipid oxides from the hydroxyl radical oxidation that causes the structural distortions of the liposomes.

Stiffening Effect of Ceramide on Lipid Membranes Provides Non-Sacrificial Protection against Potent Chemical Damage.

Ceramide is a sphingolipid that constitutes only a small fraction of membrane biomolecules but plays a central role in regulating many biological processes. The ceramide level in cell membranes can drastically increase in response to external damage, which has been hypothesized to involve ceramide's biophysical role that increases the membrane packing density and lowers the membrane permeability. However, direct observation of the consequent influence on membrane chemistry resulting from these ceramide-induced physical properties has been absent. Using our unique field-induced droplet ionization mass spectrometry technique combined with molecular dynamics simulations, here we report that the addition of ceramide to POPC monolayer membranes at the air-water interface greatly reduces the chemical damage from potent chemicals, •OH radicals, and HCl vapor, by stiffening the membrane packing and lowering the permeability. These results shed new light on the underlying chemoprotective role of ceramide in lipid membranes, which might serve as a previously unknown protection mechanism in response to external stimuli that cause cell stress or death.

A Targeted Photosensitizer Mediated by Visible Light for Efficient Therapy of Bacterial Keratitis.

Bacterial keratitis is a serious bacterial infection of the cornea that can cause sight loss in severe cases because of the sharp decline of efficacious antibiotics. Herein, a targeted photosensitizer based on BODIPY severing as a photobactericidal agent was developed for treating bacterial keratitis. The water solubility of the material was as high as 10 mg/mL, which was attributable to the introduction of pathogen-targeting galactose and fucose. The photosensitizer was able to preferentially bind Pseudomonas aeruginosa instead of mammalian cells and trigger the aggregation of bacteria, which ultimately facilitated effective pathogen ablation upon the generation of reactive oxygen species (ROS) via laser irradiation. Photoexcited targeted photosensitizers can promote wound healing by eradicating P. aeruginosa in rat eyes and reducing the inflammatory response, thus exhibiting the significant therapeutic effect on bacterial keratitis. We also performed molecular level mechanistic studies using the unique field-induced droplet ionization mass spectrometry methodology and confirmed that the generated ROS were mainly singlet oxygen that caused lipid peroxidation (Type II mechanism). We anticipate that the targeted photosensitizer will have great potential in the application of clinical photodynamic therapy to ocular infection.

Unravelling Melatonin's Varied Antioxidizing Protection of Membrane Lipids Determined by its Spatial Distribution.

The antioxidizing capability of membrane antioxidants is strongly affected by the submolecular regions of the membrane that they locate. However, the concurrent determination of their location in the membranes and the consequent antioxidizing effect remains difficult. Using our field-induced droplet ionization mass spectrometry methodology, here we show the rapid determination of the antioxidation effect and the spatial distribution of melatonin in POPC membranes. Melatonin effectively protects the membrane lipids against hydroxyl radicals originating from the Fenton reactions in the water phase but cannot protect the lipids against singlet oxygen generated by a lipophilic photosensitizer in the lipid tail region (oil phase). These varied antioxidizing behaviors indicate that melatonin dwells at the headgroup subregion of the membranes. We anticipate that the methodology in this study can be widely utilized in the screening of antioxidants' spatial distribution and antioxidizing efficiency, and eventually in designing novel antioxidants that could deliver specific functions.

Time-dependent optimized coupled-cluster method for multielectron dynamics. IV. Approximate consideration of the triple excitation amplitudes.

We present a cost-effective treatment of the triple excitation amplitudes in the time-dependent optimized coupled-cluster (TD-OCC) framework called TD-OCCDT(4) for studying intense laser-driven multielectron dynamics. It considers triple excitation amplitudes correct up to the fourth-order in many-body perturbation theory and achieves a computational scaling of O(N7), with N being the number of active orbital functions. This method is applied to the electron dynamics in Ne and Ar atoms exposed to an intense near-infrared laser pulse with various intensities. We benchmark our results against the TD complete-active-space self-consistent field (TD-CASSCF), TD-OCC with double and triple excitations (TD-OCCDT), TD-OCC with double excitations (TD-OCCD), and TD Hartree-Fock (TDHF) methods to understand how this approximate scheme performs in describing nonperturbatively nonlinear phenomena, such as field-induced ionization and high-harmonic generation. We find that the TD-OCCDT(4) method performs equally well as the TD-OCCDT method, almost perfectly reproducing the results of the fully correlated TD-CASSCF with a more favorable computational scaling.

Investigation of the Acid-Mediated Photosensitized Reactions of Amphiphilic α-Keto Acids at the Air–Water Interface Using Field-Induced Droplet Ionization Mass Spectrometry

The photochemistry of α-keto acids has been of great interest due to its implications in atmospheric and prebiotic chemistries. α-Keto acids with long alkyl chains are amphiphilic in nature, and they tend to partition at the air-water interface of atmospheric water droplets and add to the complexity of the chemistries therein. The air-water interface is a unique environment that plays a vital role in overall atmospheric processes. However, existing studies mostly focus on the photochemistry of α-keto acids in the bulk solution and neglect the reactions that occur at the interface. In this study, using the field-induced droplet ionization mass spectrometry methodology that is capable of selectively sampling amphiphilic molecules that reside at the air-water interface, we show that the acid-mediated photochemistry of 2-oxooctanoic acid and 2-oxoheptoic acid is highly different from those of previously reported reactions in the bulk and contributes to the formation of humic-like substances (HULIS). This work emphasizes the uniqueness of the photochemistry at the air-water interface. We anticipate that studies of atmosphere-relevant photochemistry at the air-water interface will be an avenue rich with opportunities.

Transient optical non-linearity in p-Si induced by a few cycle extreme THz field.

We study the impact of a few cycle extreme terahertz (THz) radiation (the field strength ETHz ∼1-15 MV/cm is well above the DC-field breakdown threshold) on a p-doped Si wafer. Pump-probe measurements of the second harmonic of a weak infrared probe were done at different THz field strengths. The second harmonic yield has an unusual temporal behavior and does not follow the common instantaneous response, ∝ETHz2. These findings were attributed to: (i) the lattice strain by the ponderomotive force of the extreme THz pulse at the maximal THz field strength below 6 MV/cm and (ii) the modulation of the THz field-induced impact ionization rate at the optical probe frequency (due to the modulation of the free carriers' drift kinetic energy from the probe field) at the THz field strength above 6-8 MV/cm.

Free-Radical-Initiated Phospholipid Oxidations at the Air–Water Interface: The Oxidation of Unsaturated and Saturated Fatty Acid Chains

Lipid oxidations initiated by free radicals are usually considered to undergo peroxidation, a chain process starting with hydrogen abstraction by an initiator, followed by O2 uptake. While this peroxidation mechanism is widely accepted and sometimes taken for granted, here we provide evidence of the oxidation of both of the unsaturated and saturated fatty acid chains in phospholipids initiated by photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide (TMDPO) at the air-water interface, and no peroxidation products are observed in these reactions. A unique field-induced droplet ionization mass spectrometry (FIDI-MS) methodology which is capable of the selective online sampling of monolayers of molecules that reside at the air-water interface is employed to detect the products. We have shown that the double bonds on the oleyl chains of the lipids are first oxidized into epoxides, after which other saturated carbon atoms are oxidized into carbonyl groups. We anticipate that this work will draw more attention to the complexity of the lipid oxidation chemistry initiated by free radicals.

Hyperfine splitting and lifetime of the positronium lowest level in a strong electric field

When placed in an external electric field, positronium, which already has a finite lifetime due to annihilation, becomes additionally unstable due to field-induced ionization. Calculations of the ionization rate using ab initio methods show that, compared to annihilation, it becomes dominant in the range of field strengths belonging to over-the-barrier ionization (OBI) regime. On the other hand, the hyperfine splitting of the positronium lowest level decreases in the tunnelling domain, taking at the beginning of the OBI domain a value that is about 20% lower than the field-free value. As the field strength increases further, this splitting varies rather slowly, but here an additional splitting of triplet levels occurs, whose rate is comparable to this variation. Finally, it is demonstrated that the lowest energy levels and ionization rates for the hydrogen atom and positronium, determined within the gross structure, are related to scaling transformations.

Mass spectrometry at the air-water interface

In this Young Scholar Perspective, the history, applications, and outlook of a unique methodology, field-induced droplet ionization mass spectrometry (FIDI-MS) are discussed. FIDI-MS is capable of selective in-situ sampling of molecules that reside at the air-water interface of droplets right after chemical reactions without any sample handling or transfer, and suffers minimal influence from the bulk of the solution. Its applications in studying the air-water interface chemistry in the contexts of molecular biology, atmospheric chemistry, molecular recognition, and the insights it has brought to these fields are introduced in this Perspective. Looking to the future, we anticipate that further development and applications of FIDI-MS in various fields will be an avenue rich with opportunities.

Probe-Free Direct Identification of Type I and Type II Photosensitized Oxidation Using Field-Induced Droplet Ionization Mass Spectrometry.

While Type I and Type II photosensitizers are often carefully tailored to achieve their respective advantages in treating different cancers, the identifications of the Type I and II mechanisms as such, the key reaction intermediates, and the consequent oxidation products of the substrates have never been easy. Using our unique home-built field-induced droplet ionization mass spectrometry (FIDI-MS) method that selectively samples molecules at the air-water interface, here we show the facile determination of both Type I and II mechanisms of a poster-child photosensitizer, temoporfin, without the addition of any probes. The unstable doublet radical resulting from the hydrogen abstraction by the triplet temoporfin through the Type I mechanism is captured, manifesting the in situ advantage of FIDI-MS. We anticipate that the method developed in this study can be widely utilized in the future designs of novel photosensitizers and the screening of their photosensitization mechanisms.

Field-Induced Tunneling Ionization and Terahertz-Driven Electron Dynamics in Liquid Water.

Liquid water at ambient temperature displays ultrafast molecular motions and concomitant fluctuations of very strong electric fields originating from the dipolar H2O molecules. We show that such random intermolecular fields induce the tunnel ionization of water molecules, which becomes irreversible if an external terahertz (THz) pulse imposes an additional directed electric field on the liquid. Time-resolved nonlinear THz spectroscopy maps charge separation, transport, and localization of the released electrons on a few-picosecond time scale. The highly polarizable localized electrons modify the THz absorption spectrum and refractive index of water, a manifestation of a highly nonlinear response. Our results demonstrate how the interplay of local electric field fluctuations and external electric fields allows for steering charge dynamics and dielectric properties in aqueous systems.

Beyond lipid peroxidation: Distinct mechanisms observed for POPC and POPG oxidation initiated by UV-enhanced Fenton reactions at the air-water interface.

Fenton or Fenton-like reactions are ubiquitous in nature, and the hydroxyl radicals (·OH) generated in these reactions are accountable for a plethora of oxidation processes both in the environment and in vivo. Among these oxidation reactions, lipid oxidation initiated by ·OH radicals has long been oversimplified as a peroxidation mechanism, but in reality, it is a highly complicated process that can result in a large variety of products. Using the unique field-induced droplet ionization mass spectrometry (FIDI-MS) methodology that is capable of selective sampling of amphiphilic molecules that reside at the air-water interface, here, we show distinct mechanisms from the ultraviolet (UV)-enhanced Fenton oxidations of two phospholipids, POPC and POPG, even though these two lipids possess the same functional groups that are vulnerable to ·OH attack. We postulate that it is the different packing densities that determine the permeability of ambient NO molecules into the monolayers, resulting in highly distinct reaction pathways and products. We anticipate that this work will be a wake-up call that the lipid peroxidation mechanism is sometimes taken for granted and that lipid oxidation can be subtly affected by various factors that deserves deeper investigations.

Spatial molecular interferometry via multidimensional high-harmonic spectroscopy

Interferometry is a basic tool to resolve coherent properties in a wide range of light or matter wave phenomena. In the strong-field regime, interferometry serves as a fundamental building block in revealing ultrafast electron dynamics. In this work we manipulate strong-field-driven electron trajectories and probe the coherence of a molecular wavefunction by inducing an interferometer on a microscopic level. The two arms of the interferometer are controlled by a two-colour field, while the interference pattern is read via advanced, three-dimensional high-harmonic spectroscopy. This scheme recovers the spectral phase information associated with the structure of molecular orbitals, as well as the spatial properties of the interaction itself. Zooming into one of the most fundamental strong-field phenomena—field-induced tunnel ionization—we reconstruct the angle at which the electronic wavefunction tunnels through the barrier and follow its evolution with attosecond precision. A single-molecule attosecond interferometry that can retrieve the spectral phase information associated with the structure of molecular orbitals, as well as the phase accumulated by an electron as it tunnels out, is demonstrated.