Hydrogen Atoms Research Articles

Quantification of chirality based on electric toroidal monopole.

Chirality ubiquitously appears in nature; however, its quantification remains obscure owing to the lack of microscopic description at the quantum-mechanical level. We propose a way of evaluating chirality in terms of the electric toroidal monopole, a practical entity of time-reversal even pseudoscalar (parity-odd) objects reflecting relevant electronic wave functions. For this purpose, we analyze a twisted methane molecule at the quantum-mechanical level, showing that the electric toroidal monopoles become a quantitative indicator for chirality. In the twisted methane, we clarify that the handedness of chirality corresponds to the signof the expectation value of the electric toroidal monopole and that the most important ingredient is the modulation of the spin-dependent imaginary hopping between the hydrogen atoms, while the relativistic spin-orbit coupling within the carbon atom is irrelevant for chirality.

Quantum states and static field ionization of a cylindrical confined hydrogen atom: A diffusion Monte Carlo study

AbstractIn this article, the diffusion Monte Carlo (DMC) method is applied to the study of the quantum states of a hydrogen atom confined into a cylindrical potential well. We present an independent reproduction of previous studies based on different methods, in particular the energy eigenvalues for ground and selected excited states and the polarizability of the ground state, both for finite and infinite cylinders. The static field ionization of ground and excited states of the confined atom is discussed, including the determination of the potential energy surface and equilibrium position of the proton. This study provides a further demonstration of the versatility of the DMC method for this and analogous problems.

2-in-1 Phase Space Sampling for Calculating the Absorption Spectrum of the Hydrated Electron.

The investigation of vibrational effects on absorption spectrum calculations often employs Wigner sampling or thermal sampling. While Wigner sampling incorporates zero-point energy, it may not be suitable for flexible systems. Thermal sampling is applicable to anharmonic systems yet treats nuclei classically. The application of generalized smoothed trajectory analysis (GSTA) as a postprocessing method allows for the incorporation of nuclear quantum effects (NQEs), combining the advantages of both sampling methods. We demonstrate this approach in computing the absorption spectrum of a hydrated electron. Theoretical exploration of the hydrated electron and its embryonic forms, such as water cluster anions, poses a significant challenge due to the diffusivity of the excess electron and the continuous motion of water molecules. In many previous studies, the wave nature of atomic nuclei is often neglected, despite the substantial impact of NQEs on thermodynamic and spectroscopic properties, particularly for hydrogen atoms. In our studies, we examine these NQEs for the excess electrons in various water systems. We obtained structures from mixed classical-quantum simulations for water cluster anions and the hydrated electron by incorporating the quantum effects of atomic nuclei with the filtration of the classical trajectories. Absorption spectra were determined at different theoretical levels. Our results indicate significant NQEs, red shift, and broadening of the spectra for hydrated electron systems. This study demonstrates the applicability of GSTA to complex systems, providing insights into NQEs on energetic and structural properties.

Photoredox Synthesis of Silicon-Containing Isoindolin-1-ones and Deuterated Analogues Through Hydrosilylation and Deuterium-silylation.

An efficient, practical, and metal-free protocol for the synthesis of silicon-containing isoindolin-1-ones and deuterated analogues via the synergistic combination of an organic photoredox and hydrogen atom transfer process is described. This strategy features mild reaction conditions, high atom economy, and excellent functional group compatibility, delivering a myriad of structurally diverse and valuable products with good to excellent yields.

Carboxylesterase Activatable Molecular Probe for Personalized Treatment Guidance by Analyte-Induced Molecular Transformation.

Accurate visualization of tumor microenvironment is of great significance for personalized medicine. Here, we develop a near-infrared (NIR) fluorescence/photoacoustic (FL/PA) dual-mode molecular probe (denoted as NIR-CE) for distinguishing tumors based on carboxylesterase (CE) level by an analyte-induced molecular transformation (AIMT) strategy. The recognition moiety for CE activity is the acetyl unit of NIR-CE, generating the pre-product, NIR-CE-OH, which undergoes spontaneous hydrogen atom exchange between the nitrogen atoms in the indole group and the phenol hydroxyl group, eventually transforming into NIR-CE-H. In cellular experiments and in vivo blind studies, the human hepatoma cells and tumors with high level of CE were successfully distinguished by both NIR FL and PA imaging. Our findings provide a new molecular imaging strategy for personalized treatment guidance.

Carboxylesterase Activatable Molecular Probe for Personalized Treatment Guidance by Analyte‐Induced Molecular Transformation

Accurate visualization of tumor microenvironment is of great significance for personalized medicine. Here, we develop a near‐infrared (NIR) fluorescence/photoacoustic (FL/PA) dual‐mode molecular probe (denoted as NIR‐CE) for distinguishing tumors based on carboxylesterase (CE) level by an analyte‐induced molecular transformation (AIMT) strategy. The recognition moiety for CE activity is the acetyl unit of NIR‐CE, generating the pre‐product, NIR‐CE‐OH, which undergoes spontaneous hydrogen atom exchange between the nitrogen atoms in the indole group and the phenol hydroxyl group, eventually transforming into NIR‐CE‐H. In cellular experiments and in vivo blind studies, the human hepatoma cells and tumors with high level of CE were successfully distinguished by both NIR FL and PA imaging. Our findings provide a new molecular imaging strategy for personalized treatment guidance.

Growth and Redox Properties of Boron on Al(111): Competing Affinities in the Case of Honeycomb AlB2.

The complexity of the geometric and electronic structure of boron allotropes is associated with the multicentric bonding character and the consequent B polymorphism. When growth is limited to two-dimensions (2D), the structural and electronic confinement yields the borophenes family, where the interaction with the templating substrate actually determines the stability of inequivalent boron phases. We report here a detailed study of the growth of the honeycomb AlB2 phase on Al(111), followed by an investigation of its oxidation and reduction properties. By means of a combined experimental and theoretical approach, we show that the structure of the B/Al interface is affected by the complex interplay between B, Al, and common reactive agents like oxygen and hydrogen. While kinetic effects associated with diffusion and strain release influence the AlB2 growth in vacuo, Al, B, O, and H chemical affinities determine its redox behavior. Reduction with atomic hydrogen involves the B layer and yields an ordered honeycomb borophane H/AlB2 phase. Instead, oxidation takes place at the Al interface, giving origin to buried and 1D surface aluminum oxide phases.

Influence of the Pd Oxidation State in PdNi Thin Films on Surface Acoustic Wave Hydrogen Sensing Performance.

PdNi alloy thin films demonstrate exceptional hydrogen sensing performance and exhibit significant potential for application in surface acoustic wave (SAW) hydrogen sensors. However, the long-term stability of SAW H2 sensors utilizing PdNi films as catalysts experiences a substantial decrease during operation. In this paper, X-ray photoelectron spectroscopy (XPS) is employed to investigate the failure mechanisms of PdNi thin films under operational conditions. The XPS analysis reveals that the formation of PdO species on PdNi thin films plays a crucial role in the failure of hydrogen sensing. Additionally, density functional theory (DFT) calculations indicate that hydrogen atoms encounter a diffusion energy barrier during the penetration process from the PdNiOx surface to the subsurface region. The identification of PdNi film failure mechanisms through XPS and DFT offers valuable insights into the development of gas sensors with enhanced long-term stability. Guided by these mechanisms, we propose a method to restore the hydrogen sensing response time and magnitude to a certain extent by reducing the partially oxidized surface of the PdNi alloy under a hydrogen atmosphere at 70 °C, thereby restoring Pd to its metallic state with zero valence.

FragGrow: A Web Server for Structure-Based Drug Design by Fragment Growing within Constraints.

Fragment growing is an important ligand design strategy in drug discovery. In this study, we present FragGrow, a web server that facilitates structure-based drug design by fragment growing. FragGrow offers two working modes: one for growing molecules through the direct replacement of hydrogen atoms or substructures and the other for growing via virtual synthesis. FragGrow works by searching for suitable fragments that meet a set of constraints from an indexed 3D fragment database and using them to create new compounds in 3D space. The users can set a range of constraints when searching for their desired fragment, including the fragment's ability to interact with specific protein sites; its size, topology, and physicochemical properties; and the presence of particular heteroatoms and functional groups within the fragment. We hope that FragGrow will serve as a useful tool for medicinal chemists in ligand design. The FragGrow server is freely available to researchers and can be accessed at https://fraggrow.xundrug.cn.

Triplet State Radical Chemistry: Significance of the Reaction of 3SO2 with HCOOH and HNO3.

The triplet excited states of sulfur dioxide can be accessed in the UV region and have a lifetime large enough that they can react with atmospheric trace gases. In this work, we report high level ab initio calculations for the reaction of the a3B1 and b3A2 excited states of SO2 with weak and strong acidic species such as HCOOH and HNO3, aimed to extend the chemistry reported in previous studies with nonacidic H atoms (water and alkanes). The reactions investigated in this work are very versatile and follow different kinds of mechanisms, namely, proton-coupled electron transfer (pcet) and conventional hydrogen atom transfer (hat) mechanisms. The study provides new insights into a general and very important class of excited-state-promoted reactions, opening up interesting chemical perspectives for technological applications of photoinduced H-transfer reactions. It also reveals that atmospheric triplet chemistry is more significant than previously thought.

Glory interference spectroscopy in Sr atom

Slow (meV) photoelectron imaging spectroscopy is employed in the experimental study of near-threshold photoionization of strontium atoms in the presence of an external static electric field. Specifically, the study is devoted to the glory effect, that is, the appearance of an intense peak at the center of the recorded photoelectron images, when dealing with m= 0 final ionized Stark states (m denoting the magnetic quantum number). This critical effect is formally identical to that encountered in classical scattering theory, where, for a nonzero value of the impact parameter, the zero-crossing of the deflection function leads to a divergent classical differential cross section. By recording the magnitude variation of this glory peak as a function of electron excitation energy, we observe that, besides the traces of classical origin, it also exhibits intense quantum interference and beating phenomena, above and below the zero-static-field ionization threshold. We study both, single- and two-photon ionization of Sr, thus enabling a comparison not only between the different excitation schemes, but also with an earlier work devoted to two-photon ionization of Mg atom by Kalaitzis et al (2020 Phys. Rev. A 102 033101). Our recordings are analyzed within the framework of the Harmin–Fano frame transformation Stark effect theory that is applied to both the hydrogen atom and a non-hydrogenic one simulating Sr. We discuss the various aspects of the recorded and calculated glory interference and beating structures and their ‘short time Fourier transforms’ and classify them as either atom-specific or atom independent. In particular, we verify the ‘universal’ connection between the glory oscillations above the zero-field threshold and the differences between the origin-to-detector times of flight corresponding to pairs of classical electron trajectories that end up to the image center.

Uniform Tendency of Surface Dipoles Across Silicon Doping Levels and Types of H‐Terminated Surfaces

AbstractThe termination of surface‐dangling bonds on silicon through hydrogen atoms, also known as Si–H, can achieve chemical passivation and reduce surface states in the electronic bandgap, thus altering electronic properties. Through a comprehensive study of doping levels (1014–1020 cm−3) and types (n and p), a consistent surface dipole trend induced by Si–H termination is discovered. It is achieved by redistributing surface charges and establishing thermal equilibrium with the chemical bond. To resolve this, the surface work function, surface electron affinity, and the energy difference between the valence band and the Fermi level are measured by employing the Kelvin probe, X‐ray photoelectron spectroscopy, and photoelectron yield spectroscopy methods. These findings are further validated through ab initio simulations. This finding has immense implications not only for eliminating electronic defects at semiconductor interfaces, which is crucial in microelectronics but also for developing and engineering hybrid interfaces and heterojunctions with controlled electronic properties.

Nitrogen adsorption induced surface kinetics changes of diamond growth by microwave plasma CVD

The strong temperature dependence of the contribution of nitrogen to diamond growth enhancement by microwave plasma chemical vapor deposition (MPCVD) have been firstly reported and systematically studied. Generally, an enhanced hydrogen desorption from the growing surface induced by the incorporated nitrogen atoms in diamond sublayer has been successfully used to explain the weak temperature depended growth enhancement of diamond by nitrogen addition, but cannot be employed to explain the observed strong temperature dependence of nitrogen contribution to diamond growth enhancement observed in this work. This indicates a significant change of surface kinetics of diamond growth induced by nitrogen addition should be occurred around 700 °C where a maximum value achieved. At this relative low temperature, the growing surface sites should be almost fully covered with hydrogen atoms with relative low nitrogen incorporated in the diamond. The adsorbed nitrogen may then make a contribution to promote hydrogen desorption, which is believed to play a dominant role in affecting the contribution of nitrogen. Experimental and calculation results do show that both the nitrogen adsorbed on the growing surface and incorporated in the sublayer may have different contribution to the growth rate enhancement, resulting in strong and weak temperature dependence, respectively.

Møller-Plesset Adiabatic Connection at Large Coupling Strengths for Open-Shell Systems.

We study the adiabatic connection that has as weak-coupling expansion the Møller-Plesset perturbation series, generalizing to the open-shell case previous closed-shell results for the large-coupling limit. We first focus on the hydrogen atom with fractional spins, providing results along the adiabatic connection from small to large coupling strengths. We reveal an intriguing phase diagram and an equation for the large-coupling leading order that has closed-form solutions for specific choices of its relevant quantum numbers. We then show that the hydrogen atom results provide variational estimates for the large-coupling leading terms for the general many-electron open-shell case in terms of functionals of the Hartree-Fock α-spin and β-spin densities.

N2 cleavage by silylene and formation of H2Si(μ-N)2SiH2

Fixation and functionalisation of N2 by main-group elements has remained scarce. Herein, we report a fixation and cleavage of the N ≡ N triple bond achieved in a dinitrogen (N2) matrix by the reaction of hydrogen and laser-ablated silicon atoms. The four-membered heterocycle H2Si(μ-N)2SiH2, the H2SiNN(H2) and HNSiNH complexes are characterized by infrared spectroscopy in conjunction with quantum-chemical calculations. The synergistic interaction of the two SiH2 moieties with N2 results in the formation of final product H2Si(μ-N)2SiH2, and theoretical calculations reveal the donation of electron density of Si to π* antibonding orbitals and the removal of electron density from the π bonding orbitals of N2, leading to cleave the non-polar and strong NN triple bond.

Identification, Characterization, and Electronic Structures of Interconvertible Cobalt-Oxygen TAML Intermediates.

The reaction of Li[(TAML)CoIII]·3H2O (TAML = tetraamido macrocyclic tetraanionic ligand) with iodosylbenzene at 253 K in acetone in the presence of redox-innocent metal ions (Sc(OTf)3 and Y(OTf)3) or triflic acid affords a blue species 1, which is converted reversibly to a green species 2 upon cooling to 193 K. The electronic structures of 1 and 2 have been determined by combining advanced spectroscopic techniques (X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), X-ray absorption spectroscopy/extended X-ray absorption fine structure (XAS/EXAFS), and magnetic circular dichroism (MCD)) with ab initio theoretical studies. Complex 1 is best represented as an S = 1/2 [(Sol)(TAML•+)CoIII---OH(LA)]- species (LA = Lewis/Brønsted acid and Sol = solvent), where an S = 1 Co(III) center is antiferromagnetically coupled to S = 1/2 TAML•+, which represents a one-electron oxidized TAML ligand. In contrast, complex 2, also with an S = 1/2 ground state, is found to be multiconfigurational with contributions of both the resonance forms [(H-TAML)CoIV═O(LA)]- and [(H-TAML•+)CoIII═O(LA)]-; H-TAML and H-TAML•+ represent the protonated forms of TAML and TAML•+ ligands, respectively. Thus, the interconversion of 1 and 2 is associated with a LA-associated tautomerization event, whereby H+ shifts from the terminal -OH group to TAML•+ with the concomitant formation of a terminal cobalt-oxo species possessing both singlet (SCo = 0) Co(III) and doublet (SCo = 1/2) Co(IV) characters. The reactivities of 1 and 2 at different temperatures have been investigated in oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactions to compare the activation enthalpies and entropies of 1 and 2.

Persistent currents of ultrarelativistic plasma-encased endofullerene molecules entrapping a H atom

In this work, for the first time in the relevant literature, the persistent currents (PC) and induced magnetic fields (IMF) of an endofullerene molecule entrapping a hydrogen atom, under spherical confinement, are investigated. The endofullerene molecule is enclosed within a spherical region and embedded in a plasma environment. The plasma environment is depicted with the more general exponential cosine screened Coulomb potential, and its relevant effects are analyzed by considering plasma screening parameters. The relevant model for endohedral confinement is the Woods–Saxon confinement potential, which is compatible with experimental data. The effects of various forms of C n are thoroughly elucidated via the analysis of the confinement depth, spherical shell thickness, the inner radius, and the smoothing parameters. To find the bound states in the spherically confined endofullerene, the decoupling of the second-order Dirac equation for the large and small components of the radial atomic wave functions is considered. The Dirac equation with the interaction potential is solved numerically by using the Runge–Kutta–Fehlberg method via the decoupling formalism. The influence of spin orientations on the PC and IMF is also elucidated. The effects of spherical confinement, plasma shielding, and the structural properties of the fullerene on the PC and IMF are thoroughly viewed. Moreover, under given physical conditions, the optimal ranges of these effects are determined.

Diamond-like carbon conversion surfaces for space applications

We present diamond-like carbon (DLC) conversion surfaces to detect particles with energy below 2 keV. Conversion surfaces have been widely applied in measurements of low-energy particles by instruments onboard planetary and heliophysics missions. Their effectiveness is characterized by the efficiency in changing the charge state of the incident particles while maintaining a narrow angular distribution for the reflected particles. DLC as a conversion surface coating material has high conversion efficiency. We developed a conversion surface production process that provides ultra-smooth and ultra-thin DLC conversion surfaces. The process includes substrate preparation through precision cleaning, plasma immersion ion deposition of the DLC film, and diagnostics of the film parameters. The latter includes the measurement of the coating thickness, surface roughness, and the conversion efficiency for ion beams with energy below 2 keV. The process we developed provides the DLC conversion surface coating of repeatable parameters with a mean surface roughness of 3.4 ± 0.2 Å and a mean film thickness of 46.7 ± 0.8 nm uniform across the sample area. Ion beam measurements showed a negative ion yield of 1%–2% for hydrogen atoms and 8%–15% for oxygen atoms with an angular scatter distribution of 10°–20° at full width of half maximum. These results agree with those of other conversion surface coatings in the literature. The DLC conversion surfaces presented here are implemented in the conversion surface subsystem of the Interstellar Mapping and Acceleration Probe (IMAP)-Lo instrument of the IMAP mission scheduled for launch in 2025.

Toward a direct measurement of the cosmic acceleration: The pilot observation of HI 21cm absorption line at FAST

Abstract In this study, we present findings on the detection of neutral atomic hydrogen (HI) 21cm absorption in the spectrum of PKS1413+135 at redshift $z=0.24670041$. The observations were conducted by FAST, with a spectral resolution of 10 Hz, using 10 minutes of observing time.The global spectral profile is examined by modeling the absorption line using a single Gaussian function with a resolution of 10kHz within a 2MHz bandwidth. The goal is to determine the rate of the latest cosmic acceleration by directly measuring the evolution of the redshift of HI 21cm absorption line with Hubble flow towards a common background Quasar over a decade or longer time span. This will serve as a detectable signal generated by the accelerated expansion of the Universe at redshift $z < 1$, specifically redshift drift $\dot{z}$ or the SL effect.The measured HI gas column density in this DLA system is approximately equivalent to the initial observation value, considering uncertainties in the spin temperature of a spiral host galaxy. The high signal-to-noise ratio of 57, obtained at a 10kHz resolution, strongly supports the feasibility of using the HI 21cm absorption line in DLA systems to accurately measure the redshift rate at a precision level of around $10^{-10}$ per decade.

Anti-plasticizing effect of water on prilocaine and lidocaine - the role of the hydrogen bonding pattern.

It is generally accepted that water, as an effective plasticizer, decreases the glass transition temperatures (Tgs) of amorphous drugs, potentially resulting in physical instabilities. However, recent studies suggest that water can also increase the Tgs of the amorphous forms of the drugs prilocaine (PRL) and lidocaine (LID), thus acting as an anti-plasticizer. To further understand the nature of the anti-plasticizing effect of water, interactions with different solvents and the resulting structural features of PRL and LID were investigated by Fourier transform infrared spectroscopy (FTIR) and quantum chemical simulations. Heavy water (deuterium oxides) was chosen as a solvent, as the deuterium and hydrogen atoms are electronically identical. It was found that substituting hydrogen with deuterium showed a minimal impact on the anti-plasticization of water on PRL. Ethanol and ethylene glycol were chosen as solvents to compare the hydrogen bonding patterns occurring between the hydroxyl groups of the solvents and PRL and LID. Comparison of the various Tgs showed a weaker anti-plasticizing potential of these two solvents on PRL and LID. The frequency shifts of the amide CO groups of PRL and LID due to the interactions with water, heavy water, ethanol, and ethylene glycol as observed in the FTIR spectra showed a correlation with the binding energies calculated by quantum chemical simulations. Overall, this study showed that the combination of weak hydrogen bonding and strong electrostatic contributions in hydrated PRL and LID could play an important role in inducing the anti-plasticizing effect of water on those drugs.