Isomeric Transition Research Articles

Profoxydim in Focus: A Structural Examination of Herbicide Behavior in Gas and Aqueous Phases.

This study investigates the chemical structure of profoxydim, focusing on its E-isomer, the main commercial form. The research aimed to determine the predominant tautomeric forms under various environmental conditions. Using proton and carbon-13 NMR spectroscopy alongside theoretical modeling, we examined tautomers and their conformers in different solvents (MeOD, DMSO, CDCl3, benzene) to mimic gas and aqueous phases. The findings reveal that the enolic form dominates in the gas phase, while the ketonic form prevails in aqueous environments, providing key insights into the herbicide's environmental behavior. We also observed an isomeric transition from E to Z under acidic conditions, which could affect profoxydim's reactivity in natural environments. The theoretical calculations indicated that in acidic conditions, the E and Z forms are nearly degenerate, with the E form remaining dominant in neutral environments. Additionally, QSAR models assessed the toxicity of various tautomers, revealing significant differences that could impact bioactivity and environmental fate. This research offers crucial insights into the structural dynamics of profoxydim, contributing to cyclohexanedione chemistry and the development of more effective herbicides.

Arylazo-3,5-diphenylpyrazole Derivatives: Molecular Probes Exhibiting Reversible Light-induced Phase Transitions for Energy Storage and Direct Photolithographic Patterning.

We report azopyrazole photoswitches decorated with variable N-alkyl and alkoxy chains (for hydrophobic interactions) and phenyl substituents on the pyrazoles (enabling π-π stacking), showing efficient bidirectional photoswitching and reversible light-induced phase transition (LIPT). Extensive spectroscopic, microscopic, and diffraction studies and computations confirmed the manifestation of molecular-level interactions and photoisomerization into macroscopic changes leading to the LIPT phenomena. Using differential scanning calorimetric (DSC) studies, the energetics associated with those accompanying processes were estimated. The long half-lives of Z isomers, high energy contents for isomerization and phase transitions, and the stability of phases over an extended temperature range (-60 to 80 °C) make them excellent candidates for energy storage and release applications. Remarkably, the difference in the solubility of the distinct phases in one of the derivatives allowed us to utilize it as a photoresist in photolithography applications on diverse substrates.

Laser Excitation of the ^{229}Th Nuclear Isomeric Transition in a Solid-State Host.

LiSrAlF_{6} crystals doped with ^{229}Th are used in a laser-based search for the nuclear isomeric transition. Two spectroscopic features near the nuclear transition energy are observed. The first is a broad excitation feature that produces redshifted fluorescence that decays with a timescale of a few seconds. The second is a narrow, laser-linewidth-limited spectral feature at 148.382 19(4)_{stat}(20)_{sys} nm [2020 407.3(5)_{stat}(30)_{sys} GHz] that decays with a lifetime of 568(13)_{stat}(20)_{sys} s. This feature is assigned to the excitation of the ^{229}Th nuclear isomeric state, whose energy is found to be 8.355 733(2)_{stat}(10)_{sys} eV in ^{229}Th:LiSrAlF_{6}.

Synthetic Placement of Active Sites in MFI Zeolites for Selective Toluene Methylation to para-Xylene.

Brønsted acidic zeolites are ubiquitous catalysts in fuel and chemical production. Broadening the catalytic diversity of a given zeolite requires strategies to manipulate the acid site placement at framework positions within distinct microporous locations. Here, we combine experiment and theory to elucidate how intermolecular interactions between organic structure-directing agents (OSDAs) and framework Al centers influence the placement of H+ sites in distinct void environments of MFI zeolites and demonstrate the catalytic consequences of active site location on kinetically controlled (403 K) toluene methylation to xylene regioisomers. Kinetic measurements, interpreted using mechanism-derived rate expressions and transition state theory, alongside density functional theory (DFT) calculations show that larger intersection environments similarly stabilize all three xylene isomer transition states without altering well-established aromatic substitution patterns (ortho/para/meta ∼ 60%:30%:10%), while smaller channel environments preferentially destabilize transition states that form bulkier ortho- and meta-isomers, thereby resulting in high intrinsic para-xylene selectivity (∼80%). DFT calculations reveal that the flexibility of nonconventional OSDAs (e.g., 1,4-diazabicyclo[2.2.2]octane) to reorient within MFI intersections and their ability to hydrogen-bond to form protonated complexes favor the placement of Al in smaller channel environments compared to conventional quaternary OSDAs (e.g., tetra-n-propylammonium). These molecular-level insights establish a mechanistic link between OSDA structure, active site placement, and transition state stability in MFI zeolites and provide active site design strategies that are orthogonal to crystallite design approaches harnessing complex reaction-diffusion phenomena to enhance regioisomer selectivity in the industrial production of valuable polymer precursors.

Development of nuclear de-excitation model EBITEM Ver.2

ABSTRACT The gamma de-excitation model of the general-purpose radiation transport code Particle and Heavy Ion Transport code System, called the Evaluated Nuclear Structure Data File (ENSDF)-Based Isomeric Transition and isomEr production Model (EBITEM) has been upgraded with a focus on precise neutron-capture reaction simulation. The first de-excitation subsequent to neutron capture of numerous nuclei, which was formerly simulated by a model based on the single particle model, is calculated using the Evaluated Gamma Activation File. The database used for further de-excitation, ENSDF, retrieved in 2013, was replaced with Reference Input Parameter Library 3 to consider internal conversion. The internal conversion process was interfaced with the atomic de-excitation model to assess the emission of Auger electrons and fluorescent X-rays. The spectra of gamma-rays from neutron-capture reactions calculated by the upgraded EBITEM correlate better with the evaluated cross-section data than those of the previous version.

Dynamic Metal-ligand Coordination for Fluorescence Color Regulation of Hydrazone-based Bistable Photoswitches.

Achieving effective manipulation of emission color in photoresponsive materials is crucial for various advanced photonic applications. In this study, we designed and synthesized a hydrazone compound 1, ethyl (Z)-2-(2-([2,2':6',2''-terpyridin]-4'-yl)hydrazineylidene)-2-(4-(diphenylamino)phenyl)acetate, which possesses a push-pull structure incorporating triphenylamine and terpyridine. The emission intensity of compound 1 can be repeatedly switched "off" and "on" by irradiation with visible light and UV light, which induces the isomerization transition between the Z and E forms. In addition, compound 1 is capable of changing its emission wavelength from 540 nm to 607 nm through coordination with different zinc salts in toluene/CH2Cl2 mixture (v:v = 1:1). Importantly, we have successfully achieved dynamic manipulation of fluorescence color and intensity by altering the counterions of zinc complexes and switching the isomer from Z to E. Moreover, both compound 1 and its zinc complexes demonstrate remarkable photoswitchable properties with different fluorescence colors in the thin films. Finally, these films with various fluorescence colors were used for the production of luminescent tags.

Density functional theory study of the isomerization conversion of the cluster ConMoS (n = 1–5)

AbstractTo investigate the isomerization transition of cluster ConMoS (n = 1–5), we employ density functional theory and transition state theory methods in this study. The cluster is optimized at the B3LYP/def2tzvp quantum chemical level. The results reveal eight isomerization reactions for the clusters ConMoS (n = 3, 5). Analyzing the activation energies shows a greater propensity for the isomerization transformation in the forward reaction compared to the reverse reaction. At room temperature, six isomerization transformation processes exhibit rapid conversion to the product configurations. Investigation of the equilibrium constants and application of the Arrhenius formula demonstrate that the cluster isomerization reactions are primarily driven by the forward reactions, with four reactions displaying efficient reactant to product conversion rates. Furthermore, there exists a consistent relationship between the structural complexity of the cluster and the change in entropy value. This study provides theoretical insights into reaction rates and optimization of reaction pathways, facilitating mutual validation and development between experimental and theoretical approaches.

Separation of 44mSc/44gSc Nuclear Isomers Based on After-Effects.

44gSc presents a particular interest for application in nuclear medicine for positron emission tomography (PET) due to its favorable nuclear decay properties (t1/2 = 3.97 h, Emax = 1.47 MeV, branching ratio 94.3% β+). Its nuclear isomer 44mSc (t1/2 = 58.61 h) decays by isomeric transition (IT) into 44gSc, accompanied by ≈12% of conversion electron emission, which can cause a partial release of the daughter 44gSc from the chelate complex. A 13 MeV cyclotron at TRIUMF was used to produce both 44mSc and 44gSc via the natCa(p,n)44m,gSc reaction. A 44mSc/44gSc generator was designed by using a Strata C-18E cartridge. After several tested systems, a successful separation method was developed using DOTATOC as a chelator, a Strata C-18E cartridge as a generator column, and an elution solution of 0.1 M NH4-α-HIB. The yield of the generator with the daughter 44gSc release was equal to 9.8 ± 1.0% (or ≈80% per portion of conversion). This result shows the important role of after-effects in the design of radionuclide generators. Nuclear cross-section calculations were applied using the TALYS code to allow for the determination of the most promising alternative routes for 44mSc production, which will enable the development of a full-scale 44mSc/44gSc radionuclide generator based on after-effects.

Cobalt application in repair tools for maintenance and modernisation of NPP equipment

Relevance. The research discusses the actual risks that can arise from the formation of the radioisotope cobalt 60Co from the stable isotope 59Co during radiation neutron capture, which is specific to repair work at a nuclear power plant, but these risks are poorly understood. Aim. The research aims to analyse the possibility of additional exposure to ionising radiation for the repair personnel of a nuclear power plant due to the use of a repair tool that may contain cobalt. Methodology. The physical-theoretical and analytical approaches are used in the study. Results. A certain risk has been identified as a result of the use of drills or other tools for cutting metal containing cobalt among the repair tools. The calculation (analysis) of the activation of a cobalt-containing drill bit showed that a drill bit weighing 500 g containing 8% of 59Co in the tool steel acquires a partial activity (i.e., only cobalt activity) of 5.397 × 10-8 Ci, which leads to gamma radiation with an exposure dose rate of 0.024 mSv/year. The calculations of dose rates did not consider gamma radiation from the nuclear isomeric transition 60mCo→60Co, which could only worsen the radiation risk picture (when considering other examples). Conclusions. The use of a drill bit with the cobalt content specified in the calculations (or the location of the drill bit in the vicinity of the personnel), one way or another, contributes to the personnel exposure. It is proved that the calculation was not conservative, but rather liberal, because gamma radiation from the 60mCo isomer was not considered, otherwise, the obtained numerical values would have been higher. A practical recommendation to prohibit or reduce the use of tools containing cobalt during repairs on nuclear power plant equipment was made, theoretically, given that the analytically justified need to study the issue of radiation safety is relevant and vital for the safety of NPP maintenance personnel

Below-threshold harmonic generation in gas-jets for Th-229 nuclear spectroscopy.

The generation of below-threshold harmonics in gas-jets constitutes a promising path towards optical frequency combs in the vacuum ultra-violet (VUV) spectral range. Of particular interest is the 150 nm range, which can be exploited to probe the nuclear isomeric transition of the Thorium-229 isotope. Using widely available high-power, high-repetition-rate Ytterbium-based laser sources, VUV frequency combs can be generated through the process of below-threshold harmonic generation, in particular 7th harmonic generation of 1030 nm. Knowledge about the achievable efficiencies of the harmonic generation process is crucial for the development of suitable VUV sources. In this work, we measure the total output pulse energies and conversion efficiencies of below-threshold harmonics in gas-jets in a phase-mismatched generation scheme using Argon and Krypton as nonlinear media. Using a 220 fs, 1030 nm source, we reach a maximum conversion efficiency of 1.1 × 10-5 for the 7th harmonic (147 nm) and 0.78 × 10-4 for the 5th harmonic (206 nm). In addition, we characterize the 3rd harmonic of a 178 fs, 515 nm source with a maximum efficiency of 0.3%.

Monte Carlo simulation study on simultaneous detection of neutrons and gamma-rays with a GdI3:Ce scintillator detector

Neutron detection using gadolinium (Gd) and its prompt gamma-rays is vital because of the high cross-section of Gd on thermal neutrons, thereby leading to significant interest in neutron detection with Gd-converted or Gd-loaded detector. However, simultaneous detection of neutron and gamma-rays with a Gd-loaded scintillator has been given less attention. In this study, we explored the feasibility of the GdI3:Ce detector for simultaneous detection with Monte Carlo N-Particle transport extended simulation. Furthermore, we examined the physical properties of Gd for application in the radiation field mixed with neutron and gamma-rays. Similarly, we simulated the geometry of the GdI3:Ce scintillator and its spectra obtained under various conditions. The results showed that GdI3:Ce with a thickness of 1[Formula: see text]cm is enough to absorb 90[Formula: see text] of photons with energy under 81[Formula: see text]keV. A shorter source-to-detector distance and larger detector size were superior to detecting prompt gamma-rays emitted from neutron capture, not only the gamma-rays from isomeric transition (named as general gamma-ray in this paper). Ultimately, spectra taken with the Gd3:Ce scintillator under the radiation field mixed with neutrons and gamma-ray showed gamma-ray peaks from both radio-isotopes and Gd[Formula: see text]Gd reaction, indicating the feasibility of the application of simultaneous detection.

Photopyroelectric Investigation of the trans–cis Isomerization Effect on the Nematic- Isotropic Phase Transition of a Liquid Crystalline Azobenzene

Photopyroelectric calorimetry has been applied to the study of the effects of different concentration of photo-induced cis isomeric molecules on the characteristics of the nematic – isotropic phase transition in p,p’-diheptylazobenzene (7AB) samples. The investigations could be carried out by monitoring the behavior of the thermal diffusivity over the phase transition before and during the sample irradiation with UV light of varying intensity. Among other, it is shown that the monitoring of the time dependence of the thermal diffusivity at fixed sample temperature enabled the comparative study of the dynamics of the trans–cis and cis–trans isomeric transitions. It was shown that the increasing cis isomers concentration caused an increase in the fraction of material undergoing the phase transitions and increased the cis–trans conversion rate. Finally, polarization microscopy observations of the sample texture, which could be carried out together with the calorimetric evaluations proved useful for a more comprehensive analysis of the obtained results.

Atlas of nuclear isomers—Second edition

We present an updated version of the 2015-Atlas of Nuclear Isomers (Jain et al., 2015), compiling and evaluating experimental data for the isomers with half-life ≥ 10 ns, together with their spectroscopic properties such as excitation-energies, half-lives, decay modes, spins and parities, energies and multipolarities of isomeric transitions, along with the relevant original references in literature. The current version of Atlas presents many re-evaluated half-lives as compared to the 2015 edition, where values were referred to Nuclear Data Sheets publications, when no new data existed. The ENSDF database (Burrows, 1990), together with the XUNDL (XUNDL database, http://www.nndc.bnl.gov/ensdf/ensdf/xundl.jsp) and the NUBASE2020 (Kondev et al., 2021) databases have been consulted for completeness, yet, data from original papers from journals were considered in the present evaluation, and the NSR bibliographic database (Pritychenko et al., 2011) has been searched to ensure that this work is as complete and current as possible. Several useful systematic features of nuclear isomers covered in this Atlas have been discussed. Literature cutoff date for the extraction of data is October 31, 2022.

An Examination of Thermal Coupling of an Ir/Au TES for TORIO-229 Experiment

The TORIO-229 experiment aims for a direct model-independent determination of the transition energy of ^mathrm {229m}Th produced in ^mathrm {233}U alpha decay. This knowledge will be of interest for the development of a scientific clock exploiting the thorium isomeric state, which would be able to significantly surpass the precision of the presently best clocks. As a detector for the isomeric transition, it is planned to use an array of fast transition-edge sensors (TESs) which demonstrated to be feasible in our previous work where the Ir/Au TES prototype demonstrated 4.6pm 1.7 µs rise time, 5.8pm 2.1 µs fall time and 0.789pm 0.023 eV energy resolution and signal-to-noise ratio of sim10 with one-photon (2.824 eV) signal, satisfying the experimental requirements. Such a microcalorimeter will allow to register the transition in every possible channel in the energy range from 3 to 50 eV and with a lifetime of > 5 µs. To have a full characterization of a single TES for the final detector array design, its thermal conductance has to be measured. In this contribution, we report on a test measurement of thermal coupling of a TORIO-229 prototype-like iridium-gold TES.

Beta-Ray-Bremsstrahlung Contributions to Short-Lived Delayed Photoneutron Groups in Heavy Water Reactors

Hard bremsstrahlung produced during the deceleration of fission-product beta rays in nuclear fuel is proposed as a source of delayed photoneutrons (PNs) in heavy water reactors. Electron Gamma Shower (EGS5) code simulations of coupled electron-photon transport in seven fuel element geometries immersed in an infinite heavy water medium confirm high-energy beta rays produce sufficient bremsstrahlung yields with photon energies greater than the D(γ,n)1H reaction threshold such that the beta-ray contribution to an isotopic PN yield can be comparable to or greater than yields from hard gamma rays emitted during the isomeric transition of the daughter, especially for some short-lived fission products with high-intensity direct-to-ground-state beta transitions where the beta ray and antineutrino carry away the majority of the Q-value. Some fission products that do not have hard gamma rays in their decay schemes are in fact PN precursors due to the beta-ray-bremsstrahlung contribution. The lack of evaluated nuclear data for many short-lived fission products, data reliability issues of fission products with decay scheme data, cross-section library effects, and possible decay-chain/parent-feeding phenomenon are affecting the accuracy of PN group parameters derived from a small number of legacy experiments. The reanalysis of two legacy PN experiments supports the existence of a very-short-lived direct-delayed neutron group.

Ab-Initio Study of Calcium Fluoride Doped with Heavy Isotopes

Precision laser spectroscopy of the 229-thorium nuclear isomer transition in a solid-state environment would represent a significant milestone in the field of metrology, opening the door to the realization of a nuclear clock. Working toward this goal, experimental methods require knowledge of various properties of a large band-gap material, such as calcium fluoride doped with specific isotopes of the heavy elements thorium, actinium, cerium, neptunium, and uranium. By accurately determining the atomic structure of potential charge compensation schemes by using a generalized gradient approximation within the ab-initio framework of density functional theory, calculations of electric field gradients on the dopants become accessible, which cause a quadrupole splitting of the nuclear-level structure that can be probed experimentally. Band gaps and absorption coefficients in the range of the 229-thorium nuclear transition are estimated by using the G0W0 method and by solving the Bethe–Salpeter equation.

Photon Energy Storage in Strained Cyclic Hydrazones: Emerging Molecular Solar Thermal Energy Storage Compounds

The generally small Gibbs free energy difference between the Z and E isomers of hydrazone photoswitches has so far precluded their use in photon energy storing applications. Here, we report on a series of cyclic and acyclic hydrazones, which possess varied degrees of ring strain and, hence, stability of E isomers. The photoinduced isomerization and concurrent phase transition of the cyclic hydrazones from a crystalline to a liquid phase result in the storage of a large quantity of energy, comparable to that of azobenzene derivatives. We demonstrate that the macrocyclic photochrome design in combination with phase transition is a promising strategy for molecular solar thermal energy storage applications.

β - and γ -spectroscopy study of Pd119 and Ag119

Neutron-rich $^{119}\mathrm{Pd}$ nuclei were produced in fission of natural uranium, induced by 25-MeV protons. Fission fragments swiftly extracted with the Ion Guide Isotope Separation On-Line method were mass separated using a dipole magnet and a Penning trap, providing mono-isotopic samples of $^{119}\mathrm{Pd}$. Their ${\ensuremath{\beta}}^{\ensuremath{-}}$ decay was measured with $\ensuremath{\gamma}\ensuremath{\gamma}$- and $\ensuremath{\beta}\ensuremath{\gamma}$-spectroscopy methods using low-energy germanium detectors and a thin plastic scintillator. Two distinct nuclear-level structures were observed in $^{119}\mathrm{Ag}$, based on the $1/{2}^{\ensuremath{-}}$ and $7/{2}^{+}$ isomers reported previously. The ${\ensuremath{\beta}}^{\ensuremath{-}}$-decay work was complemented by a prompt-$\ensuremath{\gamma}$ study of levels in $^{119}\mathrm{Ag}$ populated in spontaneous fission of $^{252}\mathrm{Cf}$, performed using the Gammasphere array of germanium detectors. Contrary to previous suggestions, our data show that the $1/{2}^{\ensuremath{-}}$ isomer is located below the $7/{2}^{+}$ isomer and is proposed as a new ground state of $^{119}\mathrm{Ag}$ with the $7/{2}^{+}$ isomer excitation energy determined to be 33.4 keV. Our data indicate that there are two $\ensuremath{\beta}$ unstable isomers in $^{119}\mathrm{Pd}$, a proposed ground state of $^{119}\mathrm{Pd}$ with tentative spin $1/{2}^{+}$ or $3/{2}^{+}$ and a half-life of 0.88 s and the other one about 350 keV above, having spin ($11/{2}^{\ensuremath{-}}$) and a half-life of 0.85 s. The higher-energy isomer probably decays to the $1/{2}^{+}$ or $3/{2}^{+}$ ground state via a $\ensuremath{\gamma}$ cascade comprising 18.7-219.8-$\mathrm{X}$-keV transitions. The unobserved isomeric transition with energy $X\ensuremath{\approx}100$ keV probably has an $E3$ multipolarity. Its hindrance factor is significantly lower than for analogous $E3$ isomeric transitions in lighter Pd isotopes, suggesting an oblate deformation of levels in $^{119}\mathrm{Pd}$. Oblate configurations in $^{119}\mathrm{Ag}$ are discussed also.

Thermal neutron activation of a CeBr[formula omitted] gamma-ray sensor

We observed significant activation of a CeBr3 gamma-ray sensor following exposure to thermal neutrons with a fluence of 105 cm−2 over a 40-minute-long period. Following irradiation, the intrinsic background rate increased from 30 to 18,100 counts s−1. Pulse height spectra of the activated detector were collected over a 45-minute-long period following neutron irradiation, and the spectra showed evidence for radioactive decay products produced via both β decay and gamma decay of meta-stable excited states (isomeric transitions). The decay energies and half lives revealed the presence of 80Br (t1/2=17 min), 80Br* (t1/2=4.4 h), 82Br (t1/2=6.1 min), and 139Ce (t1/2=55 s). The presence of additional, longer-lived radioisotopes cannot be ruled out by our measurements. All of the observed activation products were formed via neutron capture on primary detector elements, and thus would be expected for any CeBr3 sensor exposed to similar (or higher) thermal neutron flux environments. Given the dramatic increase in intrinsic count rates that we observed following the relatively modest neutron exposure, we propose that CeBr3-based gamma-ray sensors may not be suitable for use in environments with high thermal neutron fluxes without the inclusion of a thermal neutron shield surrounding the sensor.

Direct Two-Photon Excitation of Isomeric Transition in Thorium-229 Nucleus

A possibility of the two-photon excitation of an isomeric state in a nucleus of thorium-229 has been discussed. The fluorescence intensity of the excitation is demonstrated to be identical for the irradiation of nuclei with either monochromatic light or polychromatic radiation consisting of a sequence of short lightpulses of the same intensity. The two-photon excitation of Th3+ ion in an electromagnetic trap with a focused laser beam with a wavelength of about 320 nm and power of 100 mW can lead to the absorption saturation, at which the fluorescence emission with the frequency of the transition in a nucleus is maximal. In crystals doped with Th4+ to a concentration of about 1018 cm-3 and irradiated with a laser radiation 10 W in power, the emission of several photons persecond with a wavelength of about 160 nm becomes possible.