Investigation of excitation functions of deuteron induced nuclear reactions on lead

Activation data of lead are of great importance due to the widespread applications of this element in various technological fields and to the well known adverse effects to biological systems. Use of high sensitivity radioanalytical techniques allows study of uptake, distribution and speciation. Cross sections of deuteron induced nuclear reactions on lead were measured up to 40 MeV using the standard stacked foil irradiation technique and high resolution gamma-ray spectrometry. Experimental cross sections and derived integral yields are reported for the ^natPb(d,xn)^{203,204,205,206,207}Bi, ^natPb(d,x)²⁰³Pb²⁰²Tl reactions. Only one set of experimental cross section data was found in the literature. The experimental data are analyzed and compared with the results of the theoretical model code ALICE-IPPE and with the experimental integral yield reported in the literature.     

Theoretical study of positron scattering by group 14 tetra hydrides: A quantum mechanical approach

The present work provides a comprehensive set of positron impact scattering cross sections for group 14 tetrahydrides, namely, SiH₄, GeH₄, SnH₄, and PbH₄. The well‐established spherical complex optical potential and complex scattering potential‐ionization contribution methods are modified to incorporate positron scattering in the present work to calculate various cross sections. The positronium formation channel is adequately included through an improved inelastic threshold. The energy range chosen for the direct ionization cross section is from the respective ionization potential (I) of the molecule to 5 keV. Likewise, positronium formation and total ionization cross sections are reported from the positronium formation threshold to 300 eV and 5 keV, respectively, and the total cross section is computed for an extensive energy range of 1 eV to 5 keV. The positron impact total cross section for stannane molecule is computed for the first time. A characteristic valley is observed in the total cross sections with minima close to the positronium formation threshold. Further increase of cross section signifies the opening of inelastic channels especially positronium formation. In general, a reasonable agreement is found between the present results and other comparisons, wherever available. Furthermore, this is the first report of the inelastic cross sections (direct ionization, positronium formation, and total ionization) for the present set of targets.     

Reactions of Thorium Oxide Clusters with Water: The Effects of Oxygen Content

Thorium oxide has many important applications in industry. In this article, theoretical calculations have been carried out to explore the hydrolysis reactions of the ThO_n (n=1–3) clusters. The reaction mechanisms of the O-deficient ThO and the O-rich ThO₃ are compared with the stoichiometric ThO₂. The theoretical results show good agreement with the prior experiments. It is shown that the hydrolysis mainly occurred on the singlet potential surface. The overall reactions consist of two hydrolysis steps which are all favourable in energy. The effects of oxygen content on the hydrolysis are elucidated. Interestingly, among them, the peroxo group O₂²⁻ in ThO₃ is converted to the HOO− ligand, behaving like the terminal O²⁻ in the hydrolysis which is transformed into the HO− groups. In addition, natural bond orbital (NBO) analyses were employed to further understand the bonding of the pertinent species and to interpret the differences in hydrolysis.     

Measurement of dispersion numbers for 36 and 100% tri-isoamyl phosphate solvents equilibrated with aqueous nitric acid solutions

The cross sections for the ¹¹⁸Sn (n, α)¹¹⁵Cd, ¹²⁰Sn (n, α)^117gCd and ¹²⁰Sn (n, α)^117mCd reactions have been measured in the neutron energy range of 13.5–14.6 MeV using the activation technique and a coaxial HPGe γ-ray detector. The fast neutrons were produced by the T (d, n) ⁴He reaction. The neutron energies in the measurements were determined by cross section ratios for ⁹³Nb(n,2n)^92mNb and ⁹⁰Zr(n, 2n)^89m+gZr reactions. The results of present work were discussed and compared with theoretical calculation data, measurement results found in the literature and with the comprehensive evaluation data in ENDF/B-VII.0, CENDL-3.1, JENDL-4.0 libraries.     

Dissociative recombination of electrons with molecular hydrogen ions

To a first approximation, the perturbation theory yields an explicit analytical expression for the cross section of the dissociative recombination of electrons with molecular hydrogen ions. The possible nonadiabatic transitions during the separation of the nuclei which lead to the appearance of H⁺+H^–, H(1s)+H(n=2), H(1s)+H(n=3) in finite reaction channels were considered. Numerical results are presented for the cross sections of direct and reverse reactions. The expression =4. 2 · 10^–8 T^–1/2 cm³/sec² was obtained for the recombination rate at low temperatures; this expression is in agreement with known results. Several general details of the calculation and their possible implications for the case of heavy molecular ions are discussed.     

Two‐Photon Absorption Cross‐Sections of Reference Dyes: A Critical Examination

The electronic structure and one‐ and two‐photon absorption spectra of four fluorophores, p‐bis(o‐methoxystyryl)benzene (Bis‐MSB), coumarin 307, fluorescein and rhodamine B, commonly used as reference compounds for two‐photon absorption spectra, have been theoretically calculated and compared with available experimental data. The possible reasons for the wide discrepancies in two‐photon absorption cross‐sections reported in the literature are discussed on the basis of the theoretical findings. The role of a solvent environment on the electronic one‐ and two‐photon absorption spectra is also studied. We highlight some necessary precautions that one needs to take when comparing literature results of two‐photon absorption cross‐sections.     

Fission neutron spectrum averaged cross sections for threshold reactions on arsenic

Summary We have measured the cross sections, averaged over a ²³⁵U fission neutron spectrum, for the two high threshold reactions: ⁷⁵As(n,p)^75mGe and ⁷⁵As(n,2n)⁷⁴As. The measured averaged cross sections are 0.292±0.022 mb, referred to the 3.95±0.20 mb standard for the ²⁷Al(n,p)²⁷Mg averaged cross section, and 0.371±0.032 mb referred to the 111±3 mb standard for the ⁵⁸Ni(n,p)^58m+gCo averaged cross section, respectively. The measured averaged cross sections were also evaluated semi-empirically by numerically integrating experimental differential cross section data extracted for both reactions from the current literature. The calculations were performed for four different representations of the thermal-neutron-induced ²³⁵U fission neutron spectrum. The calculated cross sections, though depending on analytical representation of the flux, agree with the measured values within the estimated uncertainties.     

Crosslinking mechanisms,structure and glass transition in phthalonitrile resins: Insight from computer multiscale simulations and experiments

The influence of crosslinking process on the resulting structural properties of phthalonitrile matrices is studied through theoretical and experimental investigations. Multiscale procedure for generating fully atomistic phthalonitrile networks with simulation of radical polymerization reactions and specific reactions of triazine formation at the mesoscale level is presented and applied to the case of phthalonitrile resin based on low‐melting monomer bis(3‐(3,4‐dicyanophenoxy)phenyl)phenyl phosphate. The structural properties of the generated networks of various conversions and with various amount of triazine are analyzed using the dissipative particle dynamics and atomistic molecular dynamics. Triazine‐containing networks are much sparser in comparison with triazine‐free ones in terms of simple cycle size. The values of density, coefficients of linear thermal expansion and glass transition temperatures (T_gs) agree with obtained experimental data, and are very similar for different crosslinking mechanisms. The dependence of T_g on conversion correlates well with the sol–gel transition in network structure. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 362–374     

A Genetic Algorithm‐Based Method for the Automatic Reduction of Reaction Mechanisms

An automatic method for the reduction of chemical kinetic mechanisms under specific physical or thermodynamic conditions is presented. The method relies on the genetic algorithm search logic to gradually reduce the number of reactions from the detailed mechanism while still preserving its ability to describe the overall chemistry at an acceptable error. Accuracy of the reduced mechanism is determined by comparing its solution to the solution obtained with the full mechanism under the same initial and/or physical conditions. However, not only the chemical accuracy and the size of the mechanism are considered but also the time for its solution which helps to avoid stiff and slow converging mechanisms, thus preferring the fast solutions. The reduction method is demonstrated for a detailed mechanism for methane combustion, GRI‐Mech 3.0, which was reduced from 325 reactions and 53 species to 58 reactions and 26 species, and for an iron oxide formation mechanism from iron pentacarbonyl doped flames by Wlokas et al. (Int J Chem Kinet 2013, 45(8), 487–498),  originally consisting of 144 reactions and 34 species, which was reduced to 37 reactions and 24 species. The performance of the reduced mechanisms is shown for homogeneous constant pressure reactors and for burner‐stabilized flames. The results show a good agreement between reduced and full mechanisms for both the reactor and flame cases. The presented method is flexible and can be easily adjusted to either yield more accurate (but bigger) or smaller (but less accurate) reduced mechanisms, depending on the user's preference.     

Understanding and Practical Use of Ligand and Metal Exchange Reactions in Thiolate‐Protected Metal Clusters to Synthesize Controlled Metal Clusters

It is now possible to accurately synthesize thiolate (SR)‐protected gold clusters (Au_n(SR)_m) with various chemical compositions with atomic precision. The geometric structure, electronic structure, physical properties, and functions of these clusters are well known. In contrast, the ligand or metal atom exchange reactions between these clusters and other substances have not been studied extensively until recently, even though these phenomena were observed during early studies. Understanding the mechanisms of these reactions could allow desired functional metal clusters to be produced via exchange reactions. Therefore, we have studied the exchange reactions between Au_n(SR)_m and analogous clusters and other substances for the past four years. The results have enabled us to gain deep understanding of ligand exchange with respect to preferential exchange sites, acceleration means, effect on electronic structure, and intercluster exchange. We have also synthesized several new metal clusters using ligand and metal exchange reactions. In this account, we summarize our research on ligand and metal exchange reactions.     

Activation cross sections and isomeric cross section ratios for 184Os(n,2n)183m,gOs, 190Os(n,p)190m,gRe and 86Sr(n,2n)85m,gSr reactions from 13.5 to 14.8 MeV

The cross sections for the ¹⁸⁴Os(n,2n)^183m,gOs, ¹⁹⁰Os(n,p)^190m,gRe and ⁸⁶Sr(n,2n)^85m,gSr reactions and their isomeric cross section ratios σ _m /σ _g have been measured in the neutron energy range of 13.5–14.8 MeV using the activation technique. Nuclear model calculations using the code HFTT, which employs the Hauser-Feshbach (statistical model) and exciton model (precompound effects) formalisms, were undertaken to describe the formation of the products. The total cross sections for ¹⁸⁴Os(n,2n)¹⁸³Os, ¹⁹⁰Os(n,p)¹⁹⁰Re and ⁸⁶Sr(n,2n)⁸⁵Sr reactions are compared with the experimental data found in the literature, with results of published empirical formulae, with values of model calculations including the pre-equilibrium contribution, and with the evaluation data of JEFF-3.1/A or ENDF/B-VII.     

Ab initio path‐integral calculations of kinetic and equilibrium isotope effects on base‐catalyzed RNA transphosphorylation models

Detailed understandings of the reaction mechanisms of RNA catalysis in various environments can have profound importance for many applications, ranging from the design of new biotechnologies to the unraveling of the evolutionary origin of life. An integral step in the nucleolytic RNA catalysis is self‐cleavage of RNA strands by 2′‐O‐transphosphorylation. Key to elucidating a reaction mechanism is determining the molecular structure and bonding characteristics of transition state. A direct and powerful probe of transition state is measuring isotope effects on biochemical reactions, particularly if we can reproduce isotope effect values from quantum calculations. This article significantly extends the scope of our previous joint experimental and theoretical work in examining isotope effects on enzymatic and nonenzymatic 2′‐O‐transphosphorylation reaction models that mimic reactions catalyzed by RNA enzymes (ribozymes), and protein enzymes such as ribonuclease A (RNase A). Native reactions are studied, as well as reactions with thio substitutions representing chemical modifications often used in experiments to probe mechanism. Here, we report and compare results from eight levels of electronic‐structure calculations for constructing the potential energy surfaces in kinetic and equilibrium isotope effects (KIE and EIE) computations, including a “gold‐standard” coupled‐cluster level of theory [CCSD(T)]. In addition to the widely used Bigeleisen equation for estimating KIE and EIE values, internuclear anharmonicity and quantum tunneling effects were also computed using our recently developed ab initio path‐integral method, that is, automated integration‐free path‐integral method. The results of this work establish an important set of benchmarks that serve to guide calculations of KIE and EIE for RNA catalysis. © 2014 Wiley Periodicals, Inc.     

The kinetics and mechanisms of elementary NF2 reactions with O and N atoms

A combined EPR–LMR spectrometer with a fast-flow system has been used to investigate the kinetics and mechanisms of NF₂ reactions with O and N atoms at 298 K. The overall rate constants of these reactions are: k₀ = (2.8 ± 0.4) × 10^?11 cm³/s and k_N = (5.7 ± 0.8) × 10^?11 cm³/s. The stoichiometry of the reactions with respect to O, N, NF₂, F, and NO has been determined. The statistical theory of bimolecular reactions has been used for interpretation of the results obtained.     

Water Vapor Does Not Catalyze the Reaction between Methanol and OH Radicals

Recent reports [Jara‐Toro et al., Angew. Chem. Int. Ed. 2017 , 56, 2166 and PCCP 2018 , 20, 27885] suggest that the rate coefficient of OH reactions with alcohols would increase by up to two times in going from dry to high humidity. This finding would have an impact on the budget of alcohols in the atmosphere and it may explain differences in measured and modeled methanol concentrations. The results were based on a relative technique carried out in a small Teflon bag, which might suffer from wall reactions. The effect was reinvestigated using a direct fluorescence probe of OH radicals, and no catalytic effect of H₂O could be found. Experiments in a Teflon bag were also carried out, but the results of Jara‐Toro et al. were not reproducible. Further theoretical calculations show that the water‐mediated reactions have negligible rates compared to the bare reaction and that even though water molecules can lower the barriers of reactions, they cannot make up for the entropy cost.     

Reactive orbital energy theory serving a theoretical foundation for the electronic theory of organic chemistry

It is established that the reactive orbital energy theory (ROET) theoretically reproduces the rule-based electronic theory diagrams of organic chemistry by a comparative study on the charge transfer natures of typical organic carbon–carbon and carbon–heteroatom bond formation reactions: aldol, Mannich, α-aminooxylation, and isogyric reactions. The ROET, which is an expansion of the reaction electronic theories (e.g., the frontier orbital theory) in terms of orbital energies, elucidates the reactive orbitals driving reactions and the charge transferability indices of the reactions. Performing the ROET analyses of these reactions shows that the charge transfer directions given in the rule-based diagrams of the electronic theory are reproduced even for the functional groups of charge transfer destinations in all but only two processes for 38 reaction processes. The ROET analyses also make clear the detailed orbital-based pictures of these bond formation reactions: that is, the use of the out-of-plane antibonding π orbitals in acidic conditions (enol-mode) and in-plane antibonding π orbitals in basic conditions (enolate-mode), which explain the experimentally assumed mechanisms such as the π-bond formations in acidic conditions and σ-bond formations at α-carbons in basic conditions. Furthermore, the ROET analyses explicate that the methyl group initially accepts electrons and then donates them to the bond formations in the target reactions. It is, consequently, suggested that the ROET serves a theoretical foundation for the electronic theory of organic chemistry.     

Determination of the 54Fe(n, 2n)53gFe and 54Fe(n, 2n)53mFe cross sections averaged over a 235U fission neutron spectrum

The reaction cross sections averaged over a ²³⁵U fission neutron spectrum have been measured for the ⁵⁴Fe(n, 2n)^53gFe and ⁵⁴Fe(n, 2n)^53mFe threshold reactions. The values found are, respectively: (1.14±0.13) mb, and (0.52±0.16) mb. The measured cross sections are referred to the (111±3) mb standard cross section of the ⁵⁸Ni(n, p)^58m+gCo reaction. The (81.7±2.2) mb standard cross section value for the ⁵⁴Fe(n, p)⁵⁴Mn reaction, was also used as a monitor to check the results obtained with the Ni standard, leading to an excellent agreement.     

Triple differential cross sections in the vicinity of the (2s 2)1 S state of helium

Triple differential cross sections have been measured in the vicinity of the (2s ²)¹ S autoionising state of helium, following impact by 200 eV electrons. The scattered electron detector was set at an angle of ?12° (anti-clockwise) and the forward and backward ejected electron angular ranges scanned. The direct ionisation cross section at an ejected electron energy of 33.5 eV has been obtained and the results for the resonant ionisation of the¹ S state are presented in the Shore/Balashov parametrisation. These measurements are compared with previous experimental data and emphasise the need for new detailed theoretical calculations on the autoionisation process.     

Photonenergy‐Controlled Symmetry Breaking with Circularly Polarized Light

Circularly polarized light (CPL) is known to be a true chiral entity capable of generating absolute molecular asymmetry. However, the degree of inducible optical activity depends on the λ of the incident CPL. Exposure of amorphous films of rac‐alanine to tunable CPL led to enantiomeric excesses (ee) which not only follow the helicity but also the energy of driving electromagnetic radiation. Postirradiation analyses using enantioselective multidimensional GC revealed energy‐controlled ee values of up to 4.2 %, which correlate with theoretical predictions based on newly recorded anisotropy spectra g(λ). The tunability of asymmetric photochemical induction implies that both magnitude and sign can be fully controlled by CPL. Such stereocontrol provides novel insights into the wavelength and polarization dependence of asymmetric photochemical reactions and are highly relevant for absolute asymmetric molecular synthesis and for understanding the origins of homochirality in living matter.     

Calculation of photoionization cross sections of Na2–8 and K2–8 clusters

Analysis of free metal clusters studied with photoionization mass spectrometry or photoelectron spectroscopy requires theoretical predictions of the photoionization cross sections to gain a deeper physical understanding. Calculated energy-dependent photoionization cross sections of Na_2–8 and K_2–8 clusters are presented in this study. The ground state electronic structure of the clusters are calculated using the Local Spin Density method (LSD) which is also the starting point for the cross section calculation with the continuum multiple scattering method. A basic analysis of the photoionization process is given within the independent electron picture. Strong resonances are predicted in the UV cross sections (5–10 eV) of K_3–8 but not for Na_3–8, interpreted as shape resonances, i.e. quasibound states in which electrons are trapped by a potential barrier. Unfortunately experimental data are only known close to the ionization threshold and a comparison between our values and experimental data in a broad energy range is not possible.     

Determination of rare earth elements by charged particle activation analysis in geological materials

The rare earth elements (REE), Pr, Sm, Eu, Gd, Ho, Er and Tm have been determined by charged particle activation analysis using 40 MeV a-particles through radiochemical approach. The radiochemical separation of REE as a group has been carried out from the bulk matrix. It has been shown from the theoretical computation that the products obtained from (a,xn) reactions (x = 1, 2, 3) are more suitable compared to those from (a,pyn) reactions (y = 0, 1, 2) due to the former having higher cross section (of the order of thousand millibarns).