Measurement of Time Dependent Product Branching Ratios Indicates Two-State Reactivity in Metal Mediated Chemical Reactions

For several decades, the influence of Two State Reactivity (TSR) has been implicated in a host of reactions, but has lacked a stand-alone, definitive experimental kinetic signature identifying its occurrence....

Laser-induced fluorescence experimental spectroscopy and theoretical calculations of uranium monoxide

As a model molecule of actinide chemistry, UO molecule plays an important role in understanding the electronic structure and chemical bonding of actinide-containing species. We report a study of the laser-induced fluorescence spectra of the U16O and U18O using two-dimensional spectroscopy. Several rotationally resolved excitation spectra were investigated. Accurate molecular rotational constants and equilibrium internuclear distances were reported. Low-lying electronic states information was extracted from high resolution dispersed fluorescence spectra and analyzed by the ligand field theory model. The configuration of the ground state was determined as U2+(5f37s)O2-. The branching ratios, and the vibrational harmonic and anharmonic parameters were also obtained. Radiative lifetimes were determined by recording the time-resolved fluorescence spectroscopy. Transition dipole moments were calculated using the branching ratios and the radiative lifetimes. These findings were elucidated by using quantum-chemical calculations, and the chemical bonding was also analyzed. The findings presented in this work will enrich our understanding of actinide-containing molecules.

Strong Isotope-dependent Photodissociation Branching Ratios of N2 and Their Potential Implications for the 14N/15N Isotope Fractionation in Titan's Atmosphere

The origin and evolution of the 14N/15N ratio of Titan’s atmosphere has long been a subject of debate. Clearly a better understanding of the N isotopic fractionation mechanism would greatly help resolve this. Photodissociation of N2 by solar radiation has been suggested to either play a negligible role in fractionating the N isotopes in Titan, due to its rather low escape velocity, or to preferentially remove 15N through self-shielding controlled photochemical reactions. Here, we systematically measure the branching ratios of 14N15N between N(4S)+N(2P) and N(4S)+N(2D) channels. We find that many of its absorption states predominantly dissociate into N(4S)+N(2P) with a strong isotope effect between 14N2 and 14N15N. Since N atoms produced from N(4S)+N(2P) acquire velocities close to Titan’s escape velocity, these findings provide a new N isotope fractionation mechanism for Titan that has not been considered before, potentially providing important constraints on the origin and evolution of Titan’s N2-dominated atmosphere.

Unsupervised hadronic SUEP at the LHC

Confining dark sectors with pseudo-conformal dynamics produce SUEPs, or Soft Unclustered Energy Patterns, at colliders: isotropic dark hadrons with soft and democratic energies. We target the experimental nightmare scenario, SUEPs in exotic Higgs decays, where all dark hadrons decay promptly to SM hadrons. First, we identify three promising observables: the charged particle multiplicity, the event ring isotropy, and the matrix of geometric distances between charged tracks. Their patterns can be exploited through a cut-and-count search, supervised machine learning, or an unsupervised autoencoder. We find that the HL-LHC will probe exotic Higgs branching ratios at the per-cent level, even without a detailed knowledge of the signal features. Our techniques can be applied to other SUEP searches, especially the unsupervised strategy, which is independent of overly specific model assumptions and the corresponding precision simulations.

A tale of invisibility: constraints on new physics in b → sνν

The Belle II experiment will measure the rare decays B → Kνν and B → K∗νν with increased sensitivity which can hence be expected to serve as a very efficient probe of new physics. We calculate the relevant branching ratios in low-energy effective field theory (LEFT) including an arbitrary number of massive sterile neutrinos and discuss the expected sensitivity to the different operators. We also take into account the longitudinal polarisation fraction FL and the inclusive decay rate B → Xsνν. In our investigation we consider new physics dominantly contributing to one and two operators both for massless and massive (sterile) neutrinos. Our results show a powerful interplay of the exclusive decay rates B → Kνν and B → K∗νν, and a surprisingly large sensitivity of the inclusive decay mode to vector operators even under conservative assumptions about its uncertainty. Furthermore, the sensitivity of FL is competitive with the branching ratio of B → K∗νν in the search for new physics contributing to scalar operators and thus also complementary to B → Kνν and B → Xsνν.

A Covariant Cauchy-Schwartz Measure’s Bounding Conditions to BSM Searches

Solving for the missing masses in the Higgs resonances, it was necessary to extend, even quantitatively via an index measurable amount, the SM using a threshold related longitudinal violation procedure. The obtained expression, by being non-contributing via its non-anomalously resulting parameter, is linked to a Cauchy-Schwartz 4-scalar product ratio type of two virtual Gauge Bosons momenta in its minimal anomalous configuration, as vs. its non-anomalous internal. Changing the bounds from energy into momenta, a convexity condition appears. Such technique clarifies the perturbative e.m. fields’ extensions into perturbative and non-perturbative QCD.In applications, there is the violation of the chiral insertion by the axion into neutrinos, and the Lepton number when passing form velocity to spin resonances, such confirming the CS procedure as plus the defiance of the SM comes through their branching ratios but not their angular distributions. Further which if remaining at the same level of minimization can restore the universality of extendibility in the Higgs self-couplings.Leading into deriving the phase of K0 → π+π-, in A(∆1=2)/A(∆1=0) so a conformal skipping dynamical shift from direct CP violation of D0 → K+K- and D0 → π+π- asymmetries, in the long-short mixing concords the phase of KL → π0ννbar, solving the KOTO anomaly.

Study of Some Nuclear Properties of 170-178W Isotopes by Using Interacting Bosons Model-1

We looked into the structure of energy levels for some Tungsten isotopes W the (even-even) and electromagnetically probability transmission for it with the Model of Interacting Bosons type one (IBM-1) to evaluate the nuclear structure for Tungsten isotopes are investigated in this study (170-178W). The data was gathered using an IBM software written in the Fortran programming language The values of the parameters in this computation show that the characteristics of tungsten isotopes fall between the γ_ unstable limit O(6) and the rotational limit SU(3). The energy and branching ratios demonstrate this. The computed results are in very excellent agreement with experimental data for the isotopes under investigation.

Atmospheric photo-oxidation of myrcene: OH reaction rate constant, gas-phase oxidation products and radical budgets

The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a Large Reaction Chamber). The chemical structure of myrcene consists of one moiety that is a conjugated π system (similar to isoprene) and another moiety that is a triple-substituted olefinic unit (similar to 2-methyl-2-butene). Hydrogen shift reactions of organic peroxy radicals (RO2) formed in the reaction of isoprene with atmospheric OH radicals are known to be of importance for the regeneration of OH. Structure–activity relationships (SARs) suggest that similar hydrogen shift reactions like in isoprene may apply to the isoprenyl part of RO2 radicals formed during the OH oxidation of myrcene. In addition, SAR predicts further isomerization reactions that would be competitive with bimolecular RO2 reactions for chemical conditions that are typical for forested environments with low concentrations of nitric oxide. Assuming that OH peroxy radicals can rapidly interconvert by addition and elimination of O2 like in isoprene, bulk isomerization rate constants of 0.21 and 0.097 s−1 (T=298 K) for the three isomers resulting from the 3′-OH and 1-OH addition, respectively, can be derived from SAR. Measurements of radicals and trace gases in the experiments allowed us to calculate radical production and destruction rates, which are expected to be balanced. The largest discrepancies between production and destruction rates were found for RO2. Additional loss of organic peroxy radicals due to isomerization reactions could explain the observed discrepancies. The uncertainty of the total radical (ROx=OH+HO2+RO2) production rates was high due to the uncertainty in the yield of radicals from myrcene ozonolysis. However, results indicate that radical production can only be balanced if the reaction rate constant of the reaction between hydroperoxy (HO2) and RO2 radicals derived from myrcene is lower (0.9 to 1.6×10-11 cm3 s−1) than predicted by SAR. Another explanation of the discrepancies would be that a significant fraction of products (yield: 0.3 to 0.6) from these reactions include OH and HO2 radicals instead of radical-terminating organic peroxides. Experiments also allowed us to determine the yields of organic oxidation products acetone (yield: 0.45±0.08) and formaldehyde (yield: 0.35±0.08). Acetone and formaldehyde are produced from different oxidation pathways, so that yields of these compounds reflect the branching ratios of the initial OH addition to myrcene. Yields determined in the experiments are consistent with branching ratios expected from SAR. The yield of organic nitrate was determined from the gas-phase budget analysis of reactive oxidized nitrogen in the chamber, giving a value of 0.13±0.03. In addition, the reaction rate constant for myrcene + OH was determined from the measured myrcene concentration, yielding a value of (2.3±0.3)×10-10 cm3 s−1.

Experimental and Computational Studies on the Reactivity of Methanimine Radical Cation (H2CNH+•) and its Isomer Aminomethylene (HCNH2+•) With C2H2

Experimental and theoretical studies are presented on the reactivity of the radical cation isomers H2CNH+• (methanimine) and HCNH2+• (aminomethylene) with ethyne (C2H2). Selective isomer generation is performed via dissociative photoionization of suitable neutral precursors as well as via direct photoionization of methanimine. Reactive cross sections (in absolute scales) and product branching ratios are measured as a function of photon and collision energies. Differences between isomers’ reactivity are discussed in light of ab-initio calculations of reaction mechanisms. The major channels, for both isomers, are due to H atom elimination from covalently bound adducts to give [C3NH4]+. Theoretical calculations show that while for the reaction of HCNH2+• with acetylene any of the three lowest energy [C3NH4]+ isomers can form via barrierless and exothermic pathways, for the H2CNH+• reagent the only barrierless pathway is the one leading to the production of protonated vinyl cyanide (CH2CHCNH+), a prototypical branched nitrile species that has been proposed as a likely intermediate in star forming regions and in the atmosphere of Titan. The astrochemical implications of the results are briefly addressed.