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ispartof: FRONTIERS IN ASTRONOMY AND SPACE SCIENCES vol:8 status: published

The interplay between hydrogen and nanovoids, despite long being recognized as a central factor in hydrogen-induced damage in structural materials, remains poorly understood. Here, focusing on tungsten as a model body-centred cubic system, we explicitly demonstrate sequential adsorption of hydrogen adatoms on Wigner–Seitz squares of nanovoids with distinct energy levels. Interaction between hydrogen adatoms on nanovoid surfaces is shown to be dominated by pairwise power-law repulsion. We establish a predictive model for quantitative determination of the configurations and energetics of hydrogen adatoms in nanovoids. This model, combined with the equation of states of hydrogen gas, enables the prediction of hydrogen molecule formation in nanovoids. Multiscale simulations, performed based on our model, show good agreement with recent thermal desorption experiments. This work clarifies fundamental physics and provides a full-scale predictive model for hydrogen trapping and bubbling in nanovoids, offering long-sought mechanistic insights that are crucial for understanding hydrogen-induced damage in structural materials. A model is established to quantitatively predict hydrogen energetics and molecule formation in nanovoids of bcc metals, clarifying the trapping and bubbling mechanisms for understanding hydrogen-induced damage.

Even after roughly a century of quantum theory, there is still debate, sometimes rather contentious, as to the nature of the chemical bond—or is it bonds, or is it bonding? In this brief overview, we summarize some of the prominent approaches to this and related issues. A key focus in any interpretation must be satisfying the two requirements that the energy of a stable molecule or complex be a minimum and that the resultant Coulombic force upon each nucleus be zero. The overall kinetic energy change in molecule formation is positive.

The surfaces of interstellar and circumstellar dust grains are the sites of molecule formation, most of which, except H2, stick and form ice mantles. The study of ice evolution thus seems directly relevant for understanding our own origins, although the relation between interstellar and solar system ices remains a key question. The comparison of interstellar and solar system ices relies evidently on an accurate understanding of the composition and processes in both environments. With the accurate in situ measurements available for the comet 67P/Churyumov-Gerasimenko with the Rosetta mission, improving our understanding of interstellar ices is the more important. Here, I will address three specific questions. First, while laboratory experiments have made much progress in understanding complex organic molecule (COM) formation in the ices, the question remains, how does COM formation depend on environment and time? Second, what is the carrier of sulfur in the ices? And third, can ice absorption bands trace the processing history of the ices? Laboratory experiments, ranging from infrared spectroscopy to identify interstellar ice species, to surface experiments to determine reaction parameters in ice formation scenarios, to heating and irradiation experiments to simulate space environments, are essential to address these questions and analyze the flood of new observational data that will become available with new facilities in the next 2-10 years.

Recent transit spectra suggest organic aerosol formation in the atmosphere of sub-Neptunes. Sulfur gases are expected to be present in warm exoplanet atmospheres with high metallicity. Many aspects of the sulfur fixation process by photochemistry in planetary atmospheres are not fully understood. In this work, tholins produced in a CO2-rich atmosphere simulation experiment with H2S were analyzed with very high-resolution mass spectrometry (HRMS) that allows for searching specific molecules in addition to providing some insight on the mixture complexity. To our knowledge, this is the first experimental investigation of sulfur-bearing organic aerosol formation from irradiation of H2S at temperatures relevant to warm exoplanets. The analysis of the mass spectra shows that the soluble organic fraction of the solid particles contains over 2500 organosulfur (CHS/CHOS/CHNS/CHNOS) molecular formulas (73% of all assigned signals) within a broad mass range (from 50 to 400 u, atomic mass unit). In particular, 14 sulfuric acid derivatives were detected and 13 unique molecular formulae that could correspond to amino acid derivatives were identified. This high molecular diversity indicates a rich and active sulfur chemistry triggered by irradiation of H2S. The average elemental composition (wt%) of the soluble fraction of the particles is 40%C, 30%O, 21%S, 6%H, and 3%N, making the sulfur abundance a factor of ∼14 larger than in the initial gas composition. Our analysis of experimental simulations shows that organosulfur species are likely an important component of the haze in exoplanet atmospheres.

Small organic molecules are thought to provide building blocks for the formation of complex interstellar polycyclic aromatic hydrocarbons (PAHs). However, the underlying chemical mechanisms remain unclear, particularly concerning the role of interstellar dust. Using molecular dynamics, we simulate the chemical reaction between dehydrogenated benzene molecules in the gas phase or on the surface of an onion-like carbon nanoparticle (NP). The reaction leads to the formation of PAHs of complex structures. The size of the formed molecules is found to roughly increase with increasing temperature up to 800 K, and to be correlated with the level of dehydrogenation. Morphology analysis features the formation of large rings that contain up to 32 carbon atom at high temperature. Density functional theory (DFT) calculations are performed to search the fundamental energetic reaction pathways. The DFT results quantitatively confirm the correlation between the reactivity and the dehydrogenation level, and the formation of stable C-8 rings. Moreover, the nanostructures formed on the NP surface point to a possible layer-by-layer formation mechanism for interstellar fullerene and carbon onions., Comment: 9 figures

This article is an erratum for:[https://doi.org/10.1051/0004-6361/201937383]

Recent ALMA observations suggest that the highest velocity part of molecular protostellar jets are launched from the dust-sublimation regions of the accretion disks ($ 2e-6 Msun/yr) are predicted to be rich in molecules if warm (TK > 800 K). The molecular content of disk winds is very sensitive to the presence of dust and a mass-fraction of surviving dust as small as 1e-5 significantly increases the H2O and SiO abundances. Chemistry of high-velocity jets is a powerful tool to probe their content in dust and uncover their launching point. Models of internal shocks are required to fully exploit the current (sub-)millimeter observations and prepare future JWST observations., accepted for publication in A&A

X-ray scattering and magnetization measurements have been used to explore the extent of orbital molecule formation in a variety of $A{\mathrm{V}}_{2}{\mathrm{O}}_{4}$ vanadium oxide spinels. Zn doping suppresses the long-range order of trimer-tetramer pairs that occurs in $\mathrm{Ga}{\mathrm{V}}_{2}{\mathrm{O}}_{4}$, but disordered orbital molecules are found across most of the $\mathrm{Z}{\mathrm{n}}_{x}\mathrm{G}{\mathrm{a}}_{1\ensuremath{-}x}{\mathrm{V}}_{2}{\mathrm{O}}_{4}$ series ($0.06\ensuremath{\le}xl0.875$). Orbital molecules are not observed in the ground states of $\mathrm{Zn}{\mathrm{V}}_{2}{\mathrm{O}}_{4}, \mathrm{Mg}{\mathrm{V}}_{2}{\mathrm{O}}_{4}$, or $\mathrm{Li}{\mathrm{V}}_{2}{\mathrm{O}}_{4}$ but are likely present in $\mathrm{L}{\mathrm{i}}_{0.5}\mathrm{G}{\mathrm{a}}_{0.5}{\mathrm{V}}_{2}{\mathrm{O}}_{4}$, an analog of the former two materials. The ratio of observed to ideal values of the V-V nearest-neighbor distance has been used to rationalize these observations.

From four independent calculations using three different theoretical approaches, rate coefficients for the formation of HeH$^+$ via the radiative association of He$^+$ and H were computed. Good agreement is found between our new calculations and prior results obtained two decades ago for kinetic temperatures between $\sim$800 and 20,000 K. This finding is inconsistent with a recent claim in the literature of a wide variation in published values and establishes the robustness of our knowledge of this process for the formation of HeH$^+$. The implications of the current results to the first detection of HeH$^+$ and its modeled abundance in the planetary nebula NGC 7027 are discussed., Comment: etable of rate coefficients available

Submillimeter/far-IR spectroscopy was used to detect and quantify organic molecules sublimated after the ultraviolet photolysis (at 12 K) and warm-up (up to 300 K) of a methanol (CH3OH) ice sample. Eleven sublimated photoproducts were uniquely identified: carbon monoxide (CO), formaldehyde (H2CO), ketene (C2H2O), acetaldehyde (CH3CHO), ethylene oxide (CH2OCH2), vinyl alcohol (CH2CHOH), ethanol (CH3CH2OH), dimethyl ether (CH3OCH3), methyl formate (HCOOCH3), glycolaldehyde (HOCH2CHO), and acetone ((CH3)2CO). Two additional products were detected in the photolyzed ice by Fourier-transform infrared (FTIR) spectroscopy: carbon dioxide (CO2) and methane (CH4). The rotational temperatures and gas densities were calculated for the organics containing two or more C atoms via a rotation diagram analysis, and the gas-phase submillimeter/far-IR technique was used in tandem with mass spectrometry and FTIR spectroscopy of the ice during photolysis. The abundance ratios of the sublimated species (normalized to methanol) were compared to those observed in hot cores (Orion-KL, Sagittarius B2(N), and IRAS 16293-2422(B)) and in comets C/2014 Q2 (Lovejoy) and 67P/Churyumov–Gerasimenko.

Significance: The family of gasotransmitter molecules, nitric oxide (NO), carbon monoxide (CO), and hydrogen sulfide (H2S), has emerged as an important mediator of numerous cellular signal transduction and pathophysiological responses. As such, these molecules have been reported to influence a diverse array of biochemical, molecular, and cell biology events often impacting one another. Recent Advances: Discrete regulation of gasotransmitter molecule formation, movement, and reaction is critical to their biological function. Due to the chemical nature of these molecules, they can move rapidly throughout cells and tissues acting on targets through reactions with metal groups, reactive chemical species, and protein amino acids. Critical Issues: Given the breadth and complexity of gasotransmitter reactions, this field of research is expanding into exciting, yet sometimes confusing, areas of study with significant promise for understanding health and disease. The precise amounts of tissue and cellular...

We consider the quench of an atomic impurity via a single Rydberg excitation in a degenerate Fermi gas. The Rydberg interaction with the background gas particles induces an ultralong-range potential that binds particles to form dimers, trimers, tetramers, etc. Such oligomeric molecules were recently observed in atomic Bose-Einstein condensates. In this work, we demonstrate with a functional determinant approach that quantum statistics and fluctuations have observable spectral consequences. We show that the occupation of molecular states is predicated on the Fermi statistics, which suppresses molecular formation in an emergent molecular shell structure. At large gas densities this leads to spectral narrowing, which can serve as a probe of the quantum gas thermodynamic properties., Comment: 10 pages main text + 3 pages appendices, 7 figures main text

Thermal treatments and recipes are two critical aspects for the formation of acrylamide at ordinary household cooking conditions and industrial level. Kolompeh is a traditional Iranian cookie, and the aim of this study was to monitor acrylamide formation in four different recipes: traditional sugary Kolompeh (TSK), traditional simple Kolompeh (TSIK), industrial sugary Kolompeh (ISK), and industrial simple Kolompeh (ISIK). Along with the measurement of reducing sugars, moisture, and pH, acrylamide was quantified by gas chromatography mass spectrometry (GC-MS). Results indicated that acrylamide content was 1758, 1048, 888, and 560 μg/kg for TSK, TSIK, ISK, and ISIK, respectively, revealing that the kind of thermal treatment in combination with higher concentrations of reducing sugars were the major driver for acrylamide formation. In particular, acrylamide concentration in TSIK direct heating was 1.87 times higher than industrial indirect heating treatment, highlighting that domestic preparation of Kolompeh required a specific attention as a source of potential toxic molecule formation.

Quantum chemical cluster calculations show that reactions of C$^+$ with HCN or HNC embedded in the surface of an icy grain mantle can account for the formation of a recently detected molecule, glycolonitrile, which is considered to be an important precursor to ribonucleic compounds. Reactions of cations deposited on ice mantles with minimal kinetic energy have been found theoretically to result in previously unknown pathways to significant organic compounds in protostellar systems and the interstellar medium. In density functional theory cluster calculations involving up to 24H$_2$O, C$^+$ reacts consistently with HCN embedded in ice to yield the neutral HOCHNC radical with no barrier, along with H$_3$O+ as a byproduct. If HOCHNC then reacts with H, three species can be formed: HOCH$_2$CN (isocyanomethanol), HOCH$_2$CN (glycolonitrile), and HOCHNCH. For the C$^+$ + HNC reaction on ice, the HOCHCN and H$_2$OCCN radicals form as intermediates, the first of which is another direct precursor to glycolonitrile via H addition. In addition to characterizing reaction pathways, predictions are provided of the vibrational and electronic spectra of the HCN and HNC starting clusters and the HOCHNC ice-bound intermediate., Accepted for publication in ApJ. 5 figures. Includes supplemental information (cartesian coordinates, energies, ZPE)

In this work, water and nitric acid extractable sulphur concentrations in PM2.5 fraction of urban aerosols were determined by high-resolution continuum source electrothermal molecular absorption spectrometry using most suitable CS molecular absorption band at 258.056 nm. For this purpose, the PM2.5 airborne particulates were collected on quartz filters using a high-volume sampler (500 L/min) in Istanbul (Turkey) during six months (January–June) of two consecutive years. The instrumental and experimental parameters (pyrolysis temperature, molecule formation temperature and leaching reagents) were optimised. The validity of the method for the sulphur was tested using standard reference material and the results were found to be in the uncertainty limits of the certified value.

The formation of diatomic AlF molecules was studied in a C2H2/N2O flame by means of a high-resolution continuum source flame absorption spectrometer using different fluorine containing compounds HF, H2SiF6, HBF4 and CF3COOH as fluorine sources. The fragmentation of these fluorine sources, as well the resulting impact on the AlF molecule formation, was derived from flame height distribution studies of the atomic and molecular species Al, AlO, Si, SiO, SiF, B and BF as a function of the fluorine concentration, the molar Al:F ratio and the burner gas composition. As a consequence, the used fluorine sources HF, H2SiF6, HBF4 and CF3COOH have been divided into two major groups. The first group of fluorine sources, covering HF, H2SiF6 and HBF4, decomposes during the drying of the aerosol under the formation of AlF3, which is the dominating species for the transport of aluminium into the flame. Its decomposition into AlF results in a high sensitivity of AlF molecular absorption at low flame observation heights. The second group of fluorine sources is exemplarily given by CF3COOH. In the upper parts of the flame the cleavage of the very stable C–F bond proceeds incompletely so that the sensitivity of the AlF molecular absorption is considerably lower than that for the other fluorine sources. In consequence, the AlF molecules are formed by the reaction between the fluorine atoms and the aluminium atoms, which are transported into the flame without the aid of fluorine, presumably via oxidic and/or carbidic species. The present investigations show that the sensitivity of the AlF molecular absorption and the pathway of AlF formation depend on the chemical form of the fluorine in the studied samples.

Determination of molecular temperatures within low-temperature plasmas is critical to understanding the reactions that drive the chemistry of these systems and the mechanisms involved in plasma-surface interactions. Optical emission spectroscopy was employed to investigate gas-phase processes in H2 and CH4 inductively coupled plasma systems. Specifically, rotational temperatures (TR) have been determined for H2 d 3 Π u → a 3 Σ g + and CH A 2 Δ → X 2 Π under a variety of plasma parameter conditions. In 100% H2 plasmas, TR(H2) values are ∼500–550 K, whereas generally higher TR(H2) values (∼500–700 K) are reported for 100% CH4 plasmas. Disparities in the rotational temperature values and trends of H2 ( d 3 Π u ) between H2 and CH4 plasmas highlight the differences in H2 excitation pathways occurring in each of these two plasma systems as TR can be affected by the mechanism for molecule formation and excitation within plasma systems. As such, mixed gas CH4/H2 plasma systems were also explored to gain further insight into these mechanistic details. These results emphasize the connections between fundamental plasma properties and plasma parameters, a key component to understanding and optimizing plasma conditions for the future development of a host of plasma technologies.

Quantum dot molecules refer to nanostructures consisting of four quantum dots around a central pit. These are observed to form in Si-Ge heteroepitaxy and are considered as an alternative to quantum dots for strain relaxation. Here we use numerical simulations of a continuum model of strained heteroepitaxy to show the spontaneous formation of quantum dot molecules in thick Si 0.5 Ge 0.5 films grown on pit–patterned Si substrates. The route to their formation first involves a quantum dot in the pit, followed by removal of material from the pit to form quantum dot molecules. These molecules are formed for smaller pit widths, whereas larger pit widths tend to create a ridged surface. A mature single–walled quantum dot molecule has a typical size of about 220 nm. On reducing the wavelength of the original pit–pattern, we notice that multiple–walled quantum dot molecules form, due to the interactions with other nearby molecules. Our results broadly agree with experiment and suggest that QDM formation on patterned substrates does not necessarily have a nucleation barrier and can take place following the usual evolution of the Asaro–Tiller–Grinfeld instability.

Traditional hypotheses on the origin of bioorganic molecules are reviewed. “Miller–Urey experiment” is looked again in the recent picture of the early Earth. The presently known cooling history of the early Earth suggests rather a reasonable mechanism of organic molecule formation; i.e., the “late heavy bombardment” (LHB) of meteorites at 4.0 ~3.8 b.y.a. would have led to the chemical conditions to produce a large amount of organic molecules on the Earth’s surface. Simulation experiments of meteorite impact to ocean have confirmed the phenomena of evaporation of rock-forming minerals and of a mass production of ammonia, a precursor of amino acid, in post-impact plume.

In this chapter we outline some of the basic understanding of the chemistry that accompanies planet formation. We discuss the basic physical environment which dictates the dominant chemical kinetic pathways for molecule formation. We focus on three zones from both observational and theoretical perspectives: (1) the planet forming midplane and ice/vapor transition zones (snow-lines), (2) the warm disk surface that is shielded from radiation, which can be readily accessed by todays observational facilities, and (3) the surface photodissociation layers where stellar radiation dominates. We end with a discussion of how chemistry influences planet formation along with how to probe the link between formation and ultimate atmospheric composition for gas giants and terrestrial worlds.

Spectroscopic and photometric monitoring observations of nova Apl 2012 (V1724 Apl) were conducted at Koyama Astronomical Observatory, Fujii-Kurosaki Observatory and Bisei Astronomical Observatory. The nova was initially considered as an outbursting pre-main-sequence young stellar object. Our monitoring observations have revealed the nova to be a Fe II type classical nova. The temporal evolution of spectra and light curves of the nova were similar to those of a slow nova (e.g., V1280 Sco and V5558 Sgr). We observed no evidence of molecule formation in V1724 Aql in contrast with V2676 Oph in which dust formation occurred after the molecular formation in the nova outflow.

Aims and Objectives: Curing units in dental offices across Punjab are analyzed for a practical purpose. Materials and Methods: One thousand light-curing units regularly used by the dentists in dental offices across the state of Punjab were examined for their output intensity. Various factors include as follows: type, power of light-curing unit, material molecule formation on tip (YES/NO), diameter of guide tip, and frequency of bulb replacement. A radiometer, a magnifying glass, and a Vernier caliper were used. Data were collected and analyzed. Results: About 75.80% of dentists use light-emitting diode (LED) lights, while 24.20% utilize halogen lamps to cure dental composites. 36.60% of light-curing units of the state had light intensity below 300 mW/cm2, out of which 61.60% were quartz–tungsten–halogen (QTH) and 28.60% LED light-curing units. 17.40% of light-curing units recorded light intensity between 301 and 400 mW/cm2. 46% of light-curing units registered an output intensity of >400 mW/cm2. 79.60% of light units showed material particle buildup on light-curing tips. 62.40% of dentists never replaced the bulbs of their light-curing units. Two-third of dental the practitioners avoided infection control barriers on the tips of curing units. Conclusions: There is a deficit of knowledge among dental practitioners in Punjab regarding care of light-curing units. Dental light-curing units should be regularly checked and infection control remedies should be opted.

The basis for cluster radioactivity is the property of nuclei of light isotopes of elements heavier than lead to spontaneously form clusters—nuclei of light elements—from valence nucleons, which gives rise to asymmetric nuclear molecules. The cluster formation proceeds through successive excitation-free transfer of valence nucleons to the α particle and to subsequent light nuclei. Nuclear molecule formation is accompanied by a considerable amount of released energy, which allows quantum-mechanical penetration of the cluster through the exit Coulomb barrier.

We study the origin of the cold molecular clumps in quasar outflows, recently detected in CO and HCN emission. We first describe the physical properties of such radiation-driven outflows and show that a transition from a momentum- to an energy-driven flow must occur at a radial distance of R ~ 0.25 kpc. During this transition, the shell of swept up material fragments due to Rayleigh-Taylor instabilities, but these clumps contain little mass and are likely to be rapidly ablated by the hot gas in which they are immersed. We then explore an alternative scenario in which clumps form from thermal instabilities at R >~ 1 kpc, possibly containing enough dust to catalyze molecule formation. We investigate this processes with 3D two-fluid (gas+dust) numerical simulations of a kpc^3 patch of the outflow, including atomic and dust cooling, thermal conduction, dust sputtering, and photoionization from the QSO radiation field. In all cases, dust grains are rapidly destroyed in ~10,000 years; and while some cold clumps form at later times, they are present only as transient features, which disappear as cooling becomes more widespread. In fact, we only find a stable two-phase medium with dense clumps if we artificially enhance the QSO radiation field by a factor 100. This result, together with the complete destruction of dust grains, renders the interpretation of molecular outflows a very challenging problem., 17 pages, 12 figures, ApJ, In press

We show that radiofrequency (RF) radiation may be used to create Feshbach resonances in ultracold gases of alkali-metal atoms at desired magnetic fields that are convenient for atomic cooling and degeneracy. For the case of $^{39}$K+$^{133}$Cs, where there are no RF-free resonances in regions where Cs may be cooled to degeneracy, we show that a resonance may be created near 21~G with 69.2~MHz RF radiation. This resonance is almost lossless with circularly polarized RF, and the molecules created are long-lived even with plane-polarized RF., Final version. 5 pages, 3 figures

The stepwise and concerted reaction mechanisms of NO with CO on Pd 1 atom and Pd 4 cluster adsorbed on the MgO surface have been studied by using the DFT/B3LYP method with the embedded cluster model. The reaction barriers have been calculated by using the IMOMO method at the CCSD level. The results suggest that the rate-controlling step barrier of the NO dissociation on the supported Pd 4 cluster for the stepwise reaction mechanism is about 57 kcal/mol and lower by about 33 kcal/mol than that on the single supported Pd atom. However, the concerted reaction pathways on the single supported Pd atom and four supported Pd atoms are energetically unfavorable with the barriers of about 98 kcal/mol and 71 kcal/mol, respectively. Compared to the concerted reaction mechanism, the stepwise reaction mechanism of NO + CO is a possible pathway of CO 2 molecule formation on the supported Pd catalysts.

We investigated the formation of nuclear molecules and the occurrence of time delays in reactions of the superheavy systems 64Ni + 207Pb ( $ Z_{1}+Z_{2}=110$ ), 132Xe + 208Pb ( $ Z_{1}+Z_{2}=136$ ) and 238U + 238U ( $ Z_{1}+Z_{2}=184$ . In deep inelastic binary reactions of Ni + Pb and Xe + Pb we observed clear signatures for the formation of long-living molecule-like nuclear systems which rotate by large angles of 180 degree. The evolution of the nuclear molecules was accompanied by large energy dissipation and a strong deformation of the nuclear system. The results from the giant system U + U revealed striking similarities to the ones from Ni + Pb and Xe + Pb , showing that significant time delays still occur in the heaviest accessible systems. The experiments were performed at the velocity filter SHIP at GSI and at the VAMOS spectrometer at GANIL.

We study a quadratic-nonlinear version of the level-crossing Demkov-Kunike problem relevant to coherent molecule formation via photo- or Feshbach-association of ultracold atoms. Using an exact third-order nonlinear differential equation for the molecular state probability, we construct an approximate solution to the problem in the fast sweep regime of the strong interaction limit. The constructed approximation, defined as a solution of a first-order nonlinear equation, contains a fitting parameter which we determine through a variational procedure. The suggested approach can be interpreted as a modification of the adiabatic approximation and can further be used for the treatment of analogous nonlinear two-state problems.

The RecF pathway of Escherichia coli is important for recombinational repair of DNA breaks and gaps. Here `we reconstitute in vitro a seven-protein reaction that recapitulates early steps of dsDNA break repair using purified RecA, RecF, RecO, RecR, RecQ, RecJ, and SSB proteins, components of the RecF system. Their combined action results in processing of linear dsDNA and its homologous pairing with supercoiled DNA. RecA, RecO, RecR, and RecJ are essential for joint molecule formation, whereas SSB and RecF are stimulatory. This reconstituted system reveals an unexpected essential function for RecJ exonuclease: the capability to resect duplex DNA. RecQ helicase stimulates this processing, but also disrupts joint molecules. RecO and RecR have two indispensable functions: They mediate exchange of RecA for SSB to form the RecA nucleoprotein filament, and act with RecF to load RecA onto the SSB–ssDNA complex at processed ssDNA–dsDNA junctions. The RecF pathway has many parallels with recombinational repair in eukaryotes.

The titled reactions are theoretically studied at MP4 (SDTQ) level with 6-311++G(3df,3pd) basis set. All the possible reaction channels are considered for the first time. The most favorable reaction path in H2CO + OH is the channel of producing H2O, which is exothermic by −32.02 kcal/mol, in well agreement with reported experimental result. For H2CO + OH−, the most favorable reaction channel is for H2 molecule formation through several paths. The reaction channels for producing H2 molecule in the titled systems are proposed for the first time. H atom formation in H2CO + OH and hydrogen symmetric transition in H2CO + OH− is also evaluated at higher theory level than literatures.

Quantum chemical calculations were carried out to investigate interplay between halogen bonds and pnicogen bonds in XBr∙∙∙OFH2P∙∙∙NH3 (X = F, Cl, CN, NC, OH, and NO2) complexes at the M06-2X/aug-cc-pVDZ level. Cooperative effects are observed when halogen bonds and pnicogen bonds coexist in the same complex. These effects are analyzed in terms of geometric and energetic properties of the complexes. The mechanism of cooperative effects is analyzed in view with molecular electrostatic potential, natural bond orbital, and density difference of molecule formation analyses.

In a recent work of ours [Phys. Rev. Lett. 112, 073601 (2014)], we generalized the Power-Zineau-Woolley gauge to describe the electrodynamics of atoms in an arbitrary confined geometry. Here we complement the theory by proposing a tractable form of the polarization field to represent atomic material with well-defined intra-atomic potential. The direct electrostatic dipole-dipole interaction between the atoms is canceled. This theory yields a suitable framework to determine limitations on the light-matter coupling in quantum optical models with discernible atoms. We find that the superradiant criticality is at the border of covalent molecule formation and crystallization., 6 pages

We investigate pump-dump photoassociation of ultracold molecules with amplitude- and phase-modulated femtosecond laser pulses. For this purpose a perturbative model for the light-matter interaction is developed and combined with a genetic algorithm for adaptive feedback control of the laser pulse shapes. The model is applied to the formation of 85Rb2 molecules in a magneto-optical trap. We find for optimized pulse shapes an improvement for the formation of ground state molecules by more than a factor of 10 compared to unshaped pulses at the same pump-dump delay time, and by 40% compared to unshaped pulses at the respective optimal pump-dump delay time. Since our model yields directly the spectral amplitudes and phases of the optimized pulses, the results are directly applicable in pulse shaping experiments.