Hitting the Bull's Eye: Stable HeBeOH+ Complex.

It is now known that the heavier noble gases (Ng=Ar-Rn) show some varying degrees of reactivity with a gradual increase in reactivity along Ar-Rn. However, because of their very small size and very high ionization potential, helium and neon are the hardest targets to crack. Although few neon complexes are isolated at very low temperatures, helium needs very extreme situations like very high pressure. Here, we find that protonated BeO, BeOH+ can bind helium and neon spontaneously at room temperature. Therefore, extreme conditions like very low temperature and/or high pressure will not be required for their experimental isolation. The Ng-Be bond strength is very high for their heavier homologs and the bond strength shows a gradual increase from He to Rn. Moreover, the Ng-Be attractive energy is almost exclusively originated from the orbital interaction which is composed of one Ng(s/pσ )→BeOH+ σ-donation and two weaker Ng(pπ )→BeOH+ π-donations, except for helium. Helium uses its low-lying vacant 2p orbitals to accept π-electron density from BeOH+ . Previously, such electron-accepting ability of helium was used to explain a somewhat stronger helium bond than neon for neutral complexes. However, the present results indicate that such π-back donations are too weak in nature to decide any energetic trend between helium and neon.

Identification and characterization of inheritable structural variations induced by ion beam radiations in rice.

High energy ion beams are effective physical mutagens for mutation induction in plants. Due to their high linear energy transfer (LET) property, they are known to generate single nucleotide variations (SNVs) and insertion/deletions (InDels, <50 bp) as well as structural variations (SVs). However, due to the technical difficulties to identify SVs, studies on ion beam induced SVs by genome sequencing have so far been limited in numbers and inadequate in nature, and knowledge of SVs is scarce with regards to their characteristics. In the present study, we identified and validated SVs in six M4 plants (designated as Ar_50, Ar_100, C_150, C_200, Ne_50 and Ne_100 according to ion beam types and irradiation doses), two each induced by argon (40Ar18+), carbon (12C6+) and neon (20Ne10+) ion beams and performed in depth analyses of their characteristics. In total, 22 SVs were identified and validated, consisting of 11 deletions, 1 duplication, and 4 intra-chromosomal and 6 inter-chromosomal translocations. There were several SVs larger than 1 kbp. The SVs were distributed across the whole genome with an aggregation with SNVs and InDels only in the Ne_50 mutants. An enrichment of a 11-bp wide G-rich DNA motif 'GAAGGWGGRGG' was identified around the SV breakpoints. Three mechanisms might be involved in the SV formation, i.e., the expansion of tandem repeats, transposable element insertion, and non-allelic homologous recombination. Put together, the present study provides a preliminary view of SVs induced by Ar, C and Ne ion beam radiations, and as a pilot study, it contributes to our understanding of how SVs might form after ion beam irradiation in rice.

Tumor cytotoxicity and immunogenicity of a novel V-jet neon plasma source compared to the kINPen.

Recent research indicated the potential of cold physical plasma in cancer therapy. The plethora of plasma-derived reactive oxygen and nitrogen species (ROS/RNS) mediate diverse antitumor effects after eliciting oxidative stress in cancer cells. We aimed at exploiting this principle using a newly designed dual-jet neon plasma source (Vjet) to treat colorectal cancer cells. A treatment time-dependent ROS/RNS generation induced oxidation, growth retardation, and cell death within 3D tumor spheroids were found. In TUM-CAM, a semi in vivo model, the Vjet markedly reduced vascularized tumors' growth, but an increase of tumor cell immunogenicity or uptake by dendritic cells was not observed. By comparison, the argon-driven single jet kINPen, known to mediate anticancer effects in vitro, in vivo, and in patients, generated less ROS/RNS and terminal cell death in spheroids. In the TUM-CAM model, however, the kINPen was equivalently effective and induced a stronger expression of immunogenic cancer cell death (ICD) markers, leading to increased phagocytosis of kINPen but not Vjet plasma-treated tumor cells by dendritic cells. Moreover, the Vjet was characterized according to the requirements of the DIN-SPEC 91315. Our results highlight the plasma device-specific action on cancer cells for evaluating optimal discharges for plasma cancer treatment.

Comprehensive track-structure based evaluation of DNA damage by light ions from radiotherapy-relevant energies down to stopping.

Track structures and resulting DNA damage in human cells have been simulated for hydrogen, helium, carbon, nitrogen, oxygen and neon ions with 0.25-256 MeV/u energy. The needed ion interaction cross sections have been scaled from those of hydrogen; Barkas scaling formula has been refined, extending its applicability down to about 10 keV/u, and validated against established stopping power data. Linear energy transfer (LET) has been scored from energy deposits in a cell nucleus; for very low-energy ions, it has been defined locally within thin slabs. The simulations show that protons and helium ions induce more DNA damage than heavier ions do at the same LET. With increasing LET, less DNA strand breaks are formed per unit dose, but due to their clustering the yields of double-strand breaks (DSB) increase, up to saturation around 300 keV/µm. Also individual DSB tend to cluster; DSB clusters peak around 500 keV/µm, while DSB multiplicities per cluster steadily increase with LET. Remarkably similar to patterns known from cell survival studies, LET-dependencies with pronounced maxima around 100-200 keV/µm occur on nanometre scale for sites that contain one or more DSB, and on micrometre scale for megabasepair-sized DNA fragments.

Analysis of trace impurities in neon by a customized gas chromatography.

Excimer lasers, widely used in the semiconductor industry, are crucial for analyzing the purity of premix laser gases for the purpose of controlling stable laser output power. In this study, we designed a system for analyzing impurities in pure neon (Ne) base gas by customized GC. Impurities in pure neon (H2 and He), which cannot be analyzed at the sub-µmol/mol level using commercial GC detectors, were analyzed by a customized pulsed-discharge Ne ionization detector (PDNeD) and a pressurized injection thermal conductivity detector using Ne as the carrier gas (Pres. Inj. Ne-TCD). From the results, trace species in Ne were identified with the following detection limits: H2, 0.378µmol/mol; O2, 0.119µmol/mol; CH4, 0.880µmol/mol; CO, 0.263µmol/mol; CO2, 0.162µmol/mol (PDNeD); and He, 0.190µmol/mol (Pres. Inj. Ne-TCD). This PDNeD and pressurized injection Ne-TCD technique thus developed permit the quantification of trace impurities present in high-purity Ne.

Development of a Ne gas target for (22)Na production by proton irradiation.

The article presents the design and development of a neon gas target for the production of (22)Na using a proton beam from the room temperature cyclotron in Variable Energy Cyclotron Centre, Kolkata. The target design is made to handle a beam power of 85 W (17 MeV, 5 µA). The design is based on simulation using the computer code FLUKA for the beam dump and CFD-CFX for target cooling. The target has been successfully used for the production of (22)Na in a 6 day long 17 MeV, 5 µA proton irradiation run.

Infrared spectra and structures of the neutral and charged CrCO2 and Cr(CO2)2 isomers in solid neon.

The reactions from codeposition of laser-ablated chromium atoms with carbon dioxide in excess neon are studied by infrared absorption spectroscopy. The species formed are identified by the effects of isotopic substitution on their infrared spectra. Density functional calculations are performed to support the spectral assignments and to interpret the geometric and electronic structures of the experimentally observed species. Besides the previously reported insertion products OCrCO and O2Cr(CO)2, the one-to-one Cr(CO2) complex and the one-to-two Cr(CO2)2 complex as well as the CrOCrCO and OCCrCO3 complexes are also formed. The Cr(CO2) complex is characterized to be side-on η(2)-C,O-coordinated. The Cr(CO2)2 complex is identified to involve a side-on η(2)-C,O-coordinated CO2 and an end-on η(1)-O-coordinated CO2. OCCrCO3 is a carbonate carbonyl complex predicted to have a planar structure with a η(2)-O,O-coordinated carbonate ligand. The CrOCrCO complex is predicted to be linear with a high-spin ground state. Besides the neutral molecules, charged species are also produced. The Cr(CO2)(+) and Cr(CO2)2(+) cation complexes are characterized to have linear end-on η(1)-O-coordinated structures with blue-shifted antisymmetric CO2 stretching vibrational frequencies. The OCrCO(-) anion is bent with the Cr-O and CO stretching frequencies red-shifted from those of OCrCO neutral molecule.

Study of the Ne((3)P2) + CH3F electron-transfer reaction below 1 K.

Relatively little is known about the dynamics of electron-transfer reactions at low collision energy. We present a study of Penning ionization of ground-state methyl fluoride molecules by electronically excited neon atoms in the 13 µeV­4.8 meV (150 mK­56 K) collision energy range, using a neutral­neutral merged beam setup. Relative cross sections have been measured for three Ne((3)P2) + CH3F reaction channels by counting the number of CH3F(+), CH2F(+), and CH3(+) product ions as a function of relative velocity between the neon and methyl fluoride molecular beams. Experimental cross sections markedly deviate from the Langevin capture model at collision energies above 20 K. The branching ratios are constant. In other words, the chemical shape of the CH3F molecule, as seen by the Ne((3)P2) atom, appears not to change as the collision energy is varied, in contrast to related Ne((3)PJ) + CH3X (X = Cl and Br) reactions at higher collision energies.

Evaluation of the grand-canonical partition function using expanded Wang-Landau simulations. III. Impact of combining rules on mixtures properties.

Combining rules, such as the Lorentz-Berthelot rules, are routinely used to calculate the thermodynamic properties of mixtures using molecular simulations. Here we extend the expanded Wang-Landau simulation approach to determine the impact of the combining rules on the value of the partition function of binary systems, and, in turn, on the phase coexistence and thermodynamics of these mixtures. We study various types of mixtures, ranging from systems of rare gases to biologically and technologically relevant mixtures, such as water-urea and water-carbon dioxide. Comparing the simulation results to the experimental data on mixtures of rare gases allows us to rank the performance of combining rules. We find that the widely used Lorentz-Berthelot rules exhibit the largest deviations from the experimental data, both for the bulk and at coexistence, while the Kong and Waldman-Hagler provide much better alternatives. In particular, in the case of aqueous solutions of urea, we show that the use of the Lorentz-Berthelot rules has a strong impact on the Gibbs free energy of the solute, overshooting the value predicted by the Waldman-Hagler rules by 7%. This result emphasizes the importance of the combining rule for the determination of hydration free energies using molecular simulations.

Theoretical prediction of the linear isomers for rare gas-carbon disulfide complexes: He-CS2, Ne-CS2, and Ar-CS2.

Theoretical studies of the potential energy surfaces (PESs) and bound states are performed for rare gas-carbon disulfide complexes, He-CS2, Ne-CS2, and Ar-CS2. Three two-dimensional intermolecular PESs are constructed from ab initio data points which are calculated at the CCSD(T) level with aug-cc-pVTZ basis set supplemented with bond functions. We find that the three PESs have very similar features and each PES can be characterized by a global T-shaped minimum, two equivalent local linear minima, and the saddle points between them. The T-shaped isomer is energetically more stable than the linear isomer for each complex. The linear isomers, which have not been observed in experiment so far, are predicted from our PESs and further identified by bound state calculations. Moreover, we assign several intermolecular vibrational states for both the T-shaped and linear isomers of the three complexes via the analysis of wavefunctions. The corresponding vibrational frequencies are calculated from the bound state energies for these assigned states. These frequencies could be helpful for further experimental studies, especially for the linear isomers. We also calculate the rovibrational transition frequencies for the three T-shaped isomers and the pure rotational transition frequencies for the linear isomers, respectively. The accuracy of the PESs is validated by the good agreement between theoretical and experimental results for the rovibrational transition frequencies and spectroscopic parameters.

State-resolved diffraction oscillations imaged for inelastic collisions of NO radicals with He, Ne and Ar.

Just as light scattering from an object results in diffraction patterns, the quantum mechanical nature of molecules can lead to the diffraction of matter waves during molecular collisions. This behaviour manifests itself as rapid oscillatory structures in measured differential cross-sections, and such observable features are sensitive probes of molecular interaction potentials. However, these structures have proved challenging to resolve experimentally. Here, we use a Stark decelerator to form a beam of state-selected and velocity-controlled NO radicals and measure state-to-state differential cross-sections for inelastic collisions of NO with He, Ne and Ar atoms using velocity map imaging. The monochromatic velocity distribution of the NO beam produced scattering images with unprecedented sharpness and angular resolution, thereby fully resolving quantum diffraction oscillations. We found excellent agreement with quantum close-coupling scattering calculations for these benchmark systems.

Basis sets for the evaluation of van der Waals complex interaction energies: Ne-N2 intermolecular potential and microwave spectrum.

In order to obtain efficient basis sets for the evaluation of van der Waals complex intermolecular potentials, we carry out systematic basis set studies. For this, interaction energies at representative geometries on the potential energy surfaces are evaluated using the CCSD(T) correlation method and large polarized LPol-n and augmented polarization-consistent aug-pc-2 basis sets extended with different sets of midbond functions. On the basis of the root mean square errors calculated with respect to the values for the most accurate potentials available, basis sets are selected for fitting the corresponding interaction energies and getting analytical potentials. In this work, we study the Ne-N2 van der Waals complex and after the above procedure, the aug-pc-2-3321 and the LPol-ds-33221 basis set results are fitted. The obtained potentials are characterized by T-shaped global minima at distances between the Ne atom and the N2 center of mass of 3.39 Å, with interaction energies of -49.36 cm(-1) for the aug-pc-2-3321 surface and -50.28 cm(-1) for the LPol-ds-33221 surface. Both sets of results are in excellent agreement with the reference surface. To check the potentials further microwave transition frequencies are calculated that agree well with the experimental and the aV5Z-33221 values. The success of this study suggests that it is feasible to carry out similar accurate calculations of interaction energies and ro-vibrational spectra at reduced cost for larger complexes than has been possible hitherto.

Multiple excitation of Fuchs-Kliewer phonons by Ne⁺ ions back-scattered by the LiF(100) surface at grazing incidence.

An analytic model is developed to describe the inelastic processes occurring when keV Ne(+) ions are scattered at grazing incidence by the (100) surface of LiF. The large energy losses (up to 30 eV) of the reflected Ne(+) particles reported by Borisov et al (1999 Phys. Rev. Lett. 83 5378) are shown to arise specifically from the long-range coupling between the projectiles and the so-called Fuchs-Kliewer (FK) optical phonons of LiF whose fields extend far outside the surface. The strength of the coupling is estimated, allowing one to compute the average number of excited FK phonon quanta (hωS = 0.071 eV) and hence the mean energy losses. For emerging, neutralized Ne(0), a distinct energy loss mechanism is shown to occur, namely the excitation of FK phonons and other types of surface collective modes associated with the screening of the F(0) 'hole' left behind by the neutralization process. This mechanism contributes a large fraction of the loss, additional to that suffered by the incident Ne(+) ion. The model explains the experimental observations quantitatively (1999 Phys. Rev. Lett. 83 5378). The paper ends with a discussion of the large energy broadening of the observed loss peaks.

Measurement of the modulation transfer function of a charge-coupled device array by the combination of the self-imaging effect and slanted edge method.

In this paper, by a combination of the self-imaging effect for Ronchi gratings and the standard slanted edge modulation transfer function (MTF) measurement method for CCD cameras, the MTF of the CCD array without optics is measured. For this purpose, a Ronchi-type grating is illuminated by an expanded He-Ne laser. A self-image of the grating appears without optics on the CCD array that is located on the Talbot distance. The lines of the self-image of the grating are used as a slanted edge array. This method has all the advantages of the slanted edge method, and also since the array of the edge is ready, the total area of the CCD can be tested. The measured MTF is related to the CCD array without optics.

Ab initio potential energy surface and predicted rotational spectra for the Ne-H2O complex.

A new three-dimensional potential energy surface for the Ne-H2O complex was calculated using the coupled-cluster singles and doubles with noniterative inclusion of connected triples [CCSD(T)] with a large basis set supplemented with bond functions. The interaction energies were obtained by the supermolecular approach with the full counterpoise correction for the basis set superposition error. The CCSD(T) potential was found to have a planar T-shaped global minimum, two first-order saddle points, and a second-order saddle point. The global minimum is located at R = 3.23 Å, θ = 101.4°, and φ = 0.0° with a well depth of 64.14 cm(-1). The radial discrete variable representation∕angular finite basis representation method and the Lanczos algorithm were employed to calculate the rovibrational energy levels for four isotopic species (20)Ne-H2 (16)O, (22)Ne-H2 (16)O, (20)Ne-H2 (17)O, and (20)Ne-H2 (18)O. Rotational spectra within two internal rotor states, namely, the Σ(000) and Σ(101) states, were predicted. The average structural parameters of four Ne-H2O isotopomers on the two states were also calculated and analyzed.

Deep fracture fluids isolated in the crust since the Precambrian era.

Fluids trapped as inclusions within minerals can be billions of years old and preserve a record of the fluid chemistry and environment at the time of mineralization. Aqueous fluids that have had a similar residence time at mineral interfaces and in fractures (fracture fluids) have not been previously identified. Expulsion of fracture fluids from basement systems with low connectivity occurs through deformation and fracturing of the brittle crust. The fractal nature of this process must, at some scale, preserve pockets of interconnected fluid from the earliest crustal history. In one such system, 2.8 kilometres below the surface in a South African gold mine, extant chemoautotrophic microbes have been identified in fluids isolated from the photosphere on timescales of tens of millions of years. Deep fracture fluids with similar chemistry have been found in a mine in the Timmins, Ontario, area of the Canadian Precambrian Shield. Here we show that excesses of (124)Xe, (126)Xe and (128)Xe in the Timmins mine fluids can be linked to xenon isotope changes in the ancient atmosphere and used to calculate a minimum mean residence time for this fluid of about 1.5 billion years. Further evidence of an ancient fluid system is found in (129)Xe excesses that, owing to the absence of any identifiable mantle input, are probably sourced in sediments and extracted by fluid migration processes operating during or shortly after mineralization at around 2.64 billion years ago. We also provide closed-system radiogenic noble-gas ((4)He, (21)Ne, (40)Ar, (136)Xe) residence times. Together, the different noble gases show that ancient pockets of water can survive the crustal fracturing process and remain in the crust for billions of years.

Rotational alignment of NO (A2Σ+) from collisions with Ne.

We report the direct angle-resolved measurement of collision-induced alignment of short-lived electronically excited molecules using crossed atomic and molecular beams. Utilizing velocity-mapped ion imaging, we measure the alignment of NO in its first electronically excited state (A(2)Σ(+)) following single collisions with Ne atoms. We prepare A(2)Σ(+) (v = 0, N = 0, j = 0.5) and by comparing images obtained using orthogonal linear probe laser polarizations, we experimentally determine the degree of alignment induced by collisional rotational excitation for the final rotational states N' = 4, 5, 7, and 9. The experimental results are compared to theoretical predictions using both a simple classical hard-shell model and quantum scattering calculations on an ab initio potential energy surface (PES). The experimental results show overall trends in the scattering-angle dependent polarization sensitivity that are accounted for by the simple classical model, but structure in the scattering-angle dependence that is not. The quantum scattering calculations qualitatively reproduce this structure, and we demonstrate that the experimental measurements have the sensitivity to critique the best available potential surfaces. This sensitivity to the PES is in contrast to that predicted for ground-state NO(X) alignment.

CO2-helium and CO2-neon mixtures at high pressures.

The properties of mixtures of carbon dioxide with helium or neon have been investigated as a function of CO(2) concentration and pressure up to 30 GPa at room temperature. The binary phase diagrams of these mixtures are determined over the full range of CO(2) concentrations using visual observations and Raman scattering measurements. Both diagrams are of eutectic type, with a fluid-fluid miscibility gap for CO(2) concentrations in the range [5, 75] mol. % for He and [8, 55] mol. % for Ne, and a complete separation between the two components in the solid phase. The absence of alloys or stoichiometric compounds for these two binary systems is consistent with the Hume-Rothery rules of hard sphere mixtures. The Raman spectra and x-ray diffraction patterns of solid CO(2) embedded in He or Ne for various initial concentrations have been measured up to 30 GPa and 12 GPa, respectively. The frequencies of the Raman modes and the volume of solid phase I are identical, within error bars, to those reported for 100% CO(2) samples, thus confirming the total immiscibility of CO(2) with He and Ne in the solid phase. These results demonstrate the possibility to perform high-pressure experiments on solid CO(2) under (quasi-)hydrostatic conditions using He or Ne as pressure transmitting medium.

Cumulant expansion and analytic continuation in Monte Carlo simulation of classical Lennard-Jones clusters.

The Monte Carlo (MC) estimates of thermal averages are usually functions of system control parameters λ, such as temperature, volume, and interaction couplings. Given the MC average at a set of prescribed control parameters λ{0}, the problem of analytic continuation of the MC data to λ values in the neighborhood of λ{0} is considered in both classic and quantum domains. The key result is the theorem that links the differential properties of thermal averages to the higher order cumulants. The theorem and analytic continuation formulas expressed via higher order cumulants are numerically tested on the classical Lennard-Jones cluster system of N=13, 55, and 147 neon particles.

Tailoring of keV-ion beams by image charge when transmitting through rhombic and rectangular shaped nanocapillaries.

We report on an unexpected effect of tailoring transmission profiles of Ne(7+) ions through nanocapillaries of rhombic and rectangular cross sections in mica. We find that capillaries of rhombic cross sections produce rectangular shaped ion transmission profiles and, vice versa, that capillaries of rectangular geometry give a rhombic beam shape. This shaping effect only occurs for transmitted ions and is absent for the small fraction of neutralized particles. The experimental findings and simulations of the projectile trajectories give clear evidence that the observed effect is due to the image forces experienced by the transmitting ions. This novel beam shaping mechanism suggests applications for the guiding, focusing, and shaping of ion beams.