Study of the Energy Resolution in Alpha-Particle Spectra from Electrodeposited Radium Sources

Electrodeposited ²²⁶Ra sources were prepared and measured in order to perform a detailed study of the energy resolutions attained with two recent electrodeposition procedures for preparing spectrometric radium sources. The values of the energy resolution for the high-energy emission of ²²⁶Ra and for the single-emissions of ²¹⁰Poand ²²²Rn were calculated by fitting the data with a curve formed by the convolution of two left-handed exponentials with a Gaussian function. Significant differences between the energy resolutions for the aforementioned radionuclides were observed. The ²¹⁰Po energy resolutions were, in general, somewhat better than those obtained for ²²⁶Ra. On the contrary, the energy resolutions found for ²²²Rn were notably poorer than those obtained for ²²⁶Ra and ²¹⁰Po. These discrepancies can be satisfactorily explained by taking into consideration the distribution of these nuclides in the sources and the effect of radon diffusion involved in this type of thin deposit.     

A few remarks on the simulation and use of crystal field energy level schemes of the rare earth ions

The usefulness of the simulation of the energy level schemes of the trivalent rare earth (R³⁺) ions in the prediction of the properties of the rare earth compounds is demonstrated for a few selected cases emphasizing the connection between different spectroscopic and magnetic properties of the R³⁺ ions. The importance of the calculated energy level schemes in the UV-VUV range in interpreting complicated spectra and designing new phosphors by energy transfer and quantum cutting is described. In the absence of direct measurements, the calculated energy level values can be very useful. The possibilities to interpret the magnetic properties of the R³⁺ (and R²⁺) ions are described by using the wave functions of the energy levels obtained from the energy level simulations. As a fine example, it is shown how the amount of an Eu²⁺ impurity can be obtained from the calculation of the paramagnetic susceptibility as a function of temperature. The problems involved in the simulation of the ⁷F_J crystal field energy level scheme of the Eu³⁺ ion are highlighted by using a comparison between the extensive literature data and calculated level schemes.     

Study on the energy transfer between UO_2~(2 ) and Eu~(3 ) in sol-gel derived titania matrix by luminescence spectroscopy

The TiO2 gel doped with UO22 and Eu3 has been prepared by a sol-gel method. The quenching of the UO22 emission by Eu3 and the energy transfer from the excited state of UO22 to the ground state of Eu3 have been investigated. The energy transfer has been studied by the measurement of luminescence lifetime τ, calculations of energy transfer efficiency ηET and energy transfer rate WET. The experimental results indicated that the quenching is combined static and dynamic mechanism, but the static mechanism is dominant.     

Mobility of Li+, Na+, and Cs+ cations in Nafion membrane,as studied by NMR techniques

The local mobility and diffusion of Li⁺, Na⁺, and Cs⁺ cations in Nafion 117 membrane were explored by ⁷Li, ²³Na, and ¹³³Cs spin relaxation and pulsed field gradient NMR techniques. It was shown that the macroscopic mass transfer of cations is controlled by ion motion near sulfonate groups. Lithium and sodium cations, whose hydrated energy is higher than the water hydrogen bond energy, are moving together with water molecules, but cesium cations possessing a low hydrated energy are jumping directly between the neighboring sulfonate groups.     

Energetics of the loss of H2 from [C3H7]+

The internal energies of [C₃H₇]⁺ ions contributing to the metastable peak [C₃H₇]⁺ → [C₃H₅]⁺ + H₂ are higher (by perhaps > 100 kJ mol^?1) than those of the ion contributing to the threshold current in appearance energy measurements on [C₃H₅]⁺. The measured appearance energy may lead to an underestimation of the activation energy, i.e. negative ‘kinetic shift’, due to quantum, mechanical tunnelling. The distribution of energy released in the decomposition can be explained on the basis that much of the reverse activation energy and a statistical proportion of the excess energy is released as translation.     

Vibrational deactivation of CO2(0001) by ethane

The deactivation of CO₂(00⁰1) by ethane in the temperature range 300–600 K has been studied using a laser induced fluorescence technique. The energy transfer cross section decreased from 0.23 Ų at 300 K to 0.16 Ų at 600 K. The magnitude of the cross section is consistent with the expectation that near resonant V-V energy transfer processes are responsible for the energy transfer between CO₂(00⁰1) and ethane during collisions even though the observed temperature dependence of the energy transfer cross section does not follow that predicted by the existing theories.     

A Monte Carlo simulation of free energy relationships for the electron transfer reaction between Fe+ and Fe2+ in water

A free energy barrier ΔF^≠ = 174.2 kJ/mol for the self-exchange electron transfer reaction model Fe⁺/Fe²⁺ in water has been calculated by combining Monte Carlo simulations and the statistical perturbation theory. We have shown that, even for those electron transfer reactions that present a very high free energy barrier of activation, the free energy curve behaves parabolically versus the reaction coordinate, which justifies the quadratic expression for the activation free energy done by Marcus.     

Internal energy distributions deposited in doubly and singly charged tungsten hexacarbonyl ions generated by charge stripping,electron impact,and charge exchange

The distribution Pε of internal energies deposited in W(CO)₆ ^+?. ions upon charge stripping (that is, electron detachment to yield the doubly charged ion in the course of a single kiloelec-tronvolt energy collision) was estimated by a thermochemical method from the measured relative abundances of the doubly charged fragment ions produced. The thermochemical information needed to estimate P/ge was obtained by measuring the threshold translational energy losses associated with charge stripping of the singly charged fragment ions, W(CO) _n ⁺ (n = 0-5). The P(/ge) curve falls exponentially with increasing internal energy. The average energy transferred to W(CO)₆ ^+? upon a 7.8-keV collision with O₂ is 19 eV, yielding W(CO)₆ ^2? ions with an average of 4 eV of internal energy. In its general appearance, the P(ε) distribution associated with charge stripping is similar to the curves obtained from simple collisional activation of either W(CO) ₆ ^+?. or W(CO)₆ ^2+? in kiloelectronvolt energy gaseous collisions. Given that charge stripping occurs by way of an electronic excitation process, this similarity in the energy deposition function is taken to indicate that electronic excitation is also the major mechanism for simple collisional activation in this system at zero scattering angle in the kiloelectronvolt energy regime. The internal energy distribution associated with a related charge-stripping process, charge inversion from the metal carbonyl anions to yield the corresponding cations, was also recorded. This reaction shows a large (～7 eV) average internal energy deposition with a distribution that indicates near-zero probability of formation of unexcited ions. These data are tentatively interpreted in terms of vibrationalelectron detachment. The internal energy distribution associated with an exothermic process, charge exchange [W(CO)₆ ^2+? + O₂ → W(CO) ₊ ^6?+O₂ ^+?], was also characterized. Unexpectedly strong coupling of translational to internal energy is observed, and there is a large probability of depositing internal energies in excess of 10 eV, even though the exothermicity is only 3 eV. Finally, the internal energy distributions associated with the formation of doubly charged W(CO)₆ ^2+? ions by electron ionization have been measured. Unlike the distribution for charge stripping, but like that for singly charged ions generated by electron impact, this distribution shows considerable structure, presumably due to Franck-Condon factors.     

Evidence for a long-lived excited state of CH4+ from a beam scattering study of the collision-induced dissociation of CH4+ to CH2+ at low energy

A crossed-beam study of the collision-induced dissociation of CH₄⁺ by Ar was carried out at a center-of-mass (c.m.) collision energy of 5.5 eV. The scattering shows three patterns for the formation of CH₂⁺, (1) large-angle scattering at preferred impact parameters with little internal excitation of the products, (2) scattering near the c.m. with nearly all collision energy transferred into products internal energy and (3) superelastic scattering, i.e. conversion of internal energy to translational energy, implying the reaction is initiated by a long-lived excited state of CH₄⁺ generated by electron impact ionization of methane. No previous evidence exists, to our knowledge, that excited states of CH₄⁺ thus generated may have microsecond lifetimes.     

Maximization of Spatial Charge Density: An Approach to Ultrahigh Energy Density of Capacitive Charge Storage

Capacitive energy storage has advantages of high power density, long lifespan, and good safety, but is restricted by low energy density. Inspired by the charge storage mechanism of batteries, a spatial charge density (SCD) maximization strategy is developed to compensate this shortage by densely and neatly packing ionic charges in capacitive materials. A record high SCD (ca. 550 C cm^?3) was achieved by balancing the valance and size of charge‐carrier ions and matching the ion sizes with the pore structure of electrode materials, nearly five times higher than those of conventional ones (ca. 120 C cm^?3). The maximization of SCD was confirmed by Monte Carlo calculations, molecular dynamics simulations, and in situ electrochemical Raman spectroscopy. A full‐cell supercapacitor was further constructed; it delivers an ultrahigh energy density of 165 Wh L^?1 at a power density of 150 WL^?1 and retains 120 Wh L^?1 even at 36 kW L^?1, opening a pathway towards high‐energy‐density capacitive energy storage.     

Hartree-Fock energy curves for XΠ and Σ states of HF

Hartree-Fock energy curves have been calculated for the X²Π and ²Σ⁺ states of HF⁺ and applied to an analysis of the photoelectron spectra of HF. The ²Σ⁺ energy curve is found to have a barrier about 0.07 eV high due primarily to a repulsive ion-quadrupole interaction, and a depth of 0.37 eV. This curve will support two bound states and one shape resonance with a half-width of 0.015 eV. The energy curves are probably accurate to 0.1 eV but the analysis shows that results accurate to within 0.03 eV are required to resolve the experimental questions on the dissociation energy for the ground state of HF. The most recent experimental photoelectron results of Berkowitz (following article) encouraged a model calculation of the vibrational states of the ²Σ⁺ state. Assuming a dissociation energy of 0.45 eV and retaining the barrier three bound and one shape resonance vibrational levels are calculated for HF⁺ in agreement with the results reported by Berkowitz.     

Intermolecular interaction between squarylium cyanine and porphyrin

In this paper, the interaction between squarylium cyanine and porphyrin in chloroform is investigated by absorption and fluorescence spectroscopy. Emphasis has been put on the mechanism of intermolecular energy transfer. The overlap integral J between the absorption spectrum of squarylium cyanine and the fluorescence spectrum of porphyrin was calculated, which reveals that the singlet-singlet energy transfer may occur from porphyrin to squarylium cyanine in solution. In comparison of the observed rate constant [kqII=6.1 ×1013 (mol/L)-1·s-1] for fluorescence quenching of porphyrin by squarylium cyanine with the diffusion rate constant in chloroform [kdif=1.1×1010 (mol/L)-1·s-1] and the rate of energy transfer [ket≤6.7×104 (mol/L)-1·s-1 in the experimentally dilute solutions] estimated from Forster formula, the possibility of energy transfer by electron exchange or/and coulombic mechanism could be excluded. So it has been definitely convinced that the intermolecuiar energy transfer between them is     

Differential energy distributions in nonthermal systems: Model calculations and applications to 18F-for-F nuclear recoil substitutions in CH3CF3

A general method has been developed for the determination of the differential energy distribution in nonthermally activated reacting systems. A series of known distributions and kinetic models has been used to test this method and to determine its efficacy. Application was then made to the kinetic data of energetic CH₃CF₂ ¹⁸F formed by the substitution of F by ¹⁸F produced by nuclear recoil. The distribution obtained for this activated CH₃CF₂ ¹⁸F is seen to be highly energetic with a median energy of 137.6 kcal mol^?1 and with 33.1% of the molecules possessing energy in excess of 171 kcal mol^?1. The shape of the calculated distribution suggests that there are two mechanisms for the formation of CH₃CF₂ ¹⁸F from CH₃CF₃ and ¹⁸F, as well as that 62 kcal mol^?1 is a lower limit to the kinetic energy needed by the ¹⁸F atom for this substitution to take place.     

A New Mode of Energy Transfer between Mn2+ and Eu2+ in Nitride‐Based Phosphor SrAlSi4N7 with Tunable Light and Excellent Thermal Stability

In this work, reciprocal energy transfer between Mn²⁺ and Eu²⁺ ions in nitride SrAlSi₄N₇ has been found and investigated in detail. In contrast to Mn²⁺‐ and Eu²⁺‐activated oxide‐based phosphors, the red light centered at 608 nm is ascribed to 4f–5d transitions of Eu²⁺ ions and Mn²⁺‐activated SrAlSi₄N₇ emits a cyan light peaking at 500 nm. Additionally, the special broad excitation band of SrAlSi₄N₇:Mn²⁺ centered at 362 nm has been covered by that of Eu²⁺ ions ranging from 300 to 550 nm. The overlap of the energy level of Mn²⁺ and Eu²⁺ ions creates the conditions for reciprocal energy transfer between Eu²⁺ and Mn²⁺ ions. A series of SrAlSi₄N₇:0.002 Mn²⁺,xEu²⁺ (0≤x≤005) with tunable light emission have been synthesized and the decay curves of samples prove the reciprocal occurrence of the energy transfer between Mn²⁺ and Eu²⁺ ions. This mode of energy transfer not only prevents the loss of energy, but also improves the thermal stability, and the intensity of SrAlSi₄N₇:Mn²⁺,Eu²⁺ at 150 °C is still beyond 92 % of the initial intensity. The results provide a new mode of energy transfer, which is expected to reduce the drawbacks existing in energy transfer.     

On the Stability of Interactions between Pairs of Anions – Complexes of MCl3− (M=Be,Mg, Ca,Sr, Ba) with Pyridine and CN−

The ability of the central M atom of the MCl₃⁻ anion, with M=Be, Mg, Ca, Sr, Ba, to engage in a noncovalent bond with an approaching nucleophile is gauged by ab initio methods. The N atom of pyridine forms a M⋅⋅⋅N bond with an interaction energy between 12 and 21 kcal mol⁻¹, even though the π-hole above the M atom is not necessarily positive in sign. Despite a strong Coulombic repulsion between two anions, CN⁻ is also able to approach the M atom so as to engage in a metastable complex that is higher in energy than the individual anions. The energy barrier separating this complex from its constituent anion pair is roughly 20 kcal mol⁻¹. Despite the endothermic formation reaction energy of the CN⁻⋅⋅⋅MCl₃⁻ complex, the electron topology signals a strong interaction, more so than in pyridine⋅⋅⋅MCl₃⁻ with its exothermic binding energy. The dianionic complex is held together largely on the strength of interorbital interactions, thereby overcoming a repulsive electrostatic component. The latter is partially alleviated by the pyramidalization of the MCl₃ unit which makes its π-hole more positive. The complex sinks below the separate monomers in energy when the system is immersed in an aqueous medium, with a binding energy that varies from as much as 20 kcal mol⁻¹ for Be down to 1.2 kcal mol⁻¹ for Ba.     

Laser studies of vibrational energy transfer and relaxation of CO trapped in solid neon and argon

The infrared emission of CO trapped in solid Ne and Ar is observed at low temperature. The first vibrational level of ¹²C¹⁶O is excited by a Q-switched frequency doubled CO₂ laser. The emission spectrum consists of several lines arising from upper vibrational levels of ¹²C¹⁶O and also of ¹³C¹⁶O and ¹²C¹⁸O which are present in natural abundance. An interpretation is proposed which is based on the assumption that long range dipole—dipole interaction is the main physical process involved in these experiments. Resonance energy transfer produces an energy migration among ¹²C¹⁶O molecules without any change in vibrational populations. Phonon assisted energy transfer takes place between vibrational levels of the various isotopic species present in the solution. In order to satisfy the resonance condition a phonon is emitted or absorbed whose energy compensates for the energy mismatch between the transitions in each interacting molecule due to isotopic effect and or vibrational anharmonicity. The range of this process is greatly extended by energy migration. At the low phonon bath temperature phonon emission is much more probable than phonon absorption. So a strong excitation of upper vibrational levels with in some cases population inversions is observed.Molecular impurities act as efficient quenching centers even at very low concentration. When highly purified samples are used, the fluorescence decay time is found to be 20.6 ms in Ne and 14.5 ms in Ar and does not significantly depend upon concentration and temperature. It is concluded that radiationless relaxation is unimportant.     

Effcient Near-Infrared Quantum Cutting in Tm3+/Yb3 Codoped LiYF4 Single Crystals for Solar Photovoltaic

Downconversion (DC) with emission of two near-infrared photons about 1000 nm for each blue photon absorbed was obtained in thulium (Tm³⁺) and ytterbium (Yb³ ) codoped yt-trium lithium fluoride (LiYF₄) single crystals grown by an improved Bridgman method. The luminescent properties of the crystals were measured through photoluminescence excitation, emission spectra and decay curves. Luminescence between 960 and 1050 nm from Yb³ : ²F_5/2→²F_7/2 transition, which was originated from the DC from Tm³ ions to Yb³ ions, was observed under the excitation of blue photon at 465 nm. Moreover, the energy transfer processes were studied based on the Inokuti-Hirayama model, and the results indicated that the energy transfer from Tm³ to Yb³ was an electric dipole-dipole interaction. The max-imum quantum cutting effciency approached up to 167.5% in LiYF₄ single crystal codoped with 0.49mol% Tm³ and 5.99mol% Yb³ . Application of this crystal has prospects for increasing the energy e ciency of crystalline Si solar cells by photon doubling of the high energy part of the solar spectrum     

Production of monoenergetic MeV-range neutrons by <Superscript>3</Superscript>H(p,n)<Superscript>3</Superscript>He reaction

Monochromatic MeV-energy neutron source for secondary reaction was developed utilizing tritium embedded titanium (Ti-³H) thin film via ³H(p,n)³He reaction. We have measured the neutron energies and the energy spread by resonance reactions of ¹²C(n,tot) and ²⁸Si(n,tot). The available energy was within the range from 0.6 to 2.6 MeV. Energy spread was 1.6% at energy of 2.077 MeV. The flux in the beam direction was determined to be 3.76·10⁷ n/s/sr by irradiating ¹⁹⁷Au by about 2 MeV neutrons. This source was shown to be useful for measurements of nuclear data by measuring the total cross sections of neutrons on Fe and comparing these data to the data of ENDF-6.     

DFT studies of cation binding by ��-cyclodextrin

Interactions of the ??-cyclodextrin (??-CD) ligand with Na⁺, Cu⁺, Mg²⁺, Zn²⁺, and Al³⁺ cations were investigated using density functional theory modeling. The objective of this study was to give insight into the mechanism of cation complexation. Two groups of conformers were found. The first group preserved the initial orientation of glucopyranose residues inside the ??-CD ligand. The mutual orientation of glucopyranose residues was strongly affected by the cation in the second group of conformers. The system interaction energy was decomposed into electrostatic (ES), Pauli and orbital contributions using the Ziegler?CRauk energy partitioning scheme. The total electrostatic energy, i.e., the sum of ES energy and polarization energy, is the dominating term in the interaction energy. In vacuum, the complexes formed with Al³⁺ were found to be more stable than with di- and monocations. The vacuum stability sequence was changed in aqueous solution.     

Evaluation of Multiple Corona Reactor Modes and the Application in Odor Removal

Effects of multiple corona reactor modes on pulse characteristics, energy transfer efficiency, and odor (H₂S and NH₃) removal were investigated experimentally by the wire-plate corona reactor(s). The removal efficiency of H₂S was only 91% and the energy consumption was 16.1 Wh m⁻³ by the single mode with a gas-flow rate of 23 m³ h⁻¹ and an initial concentration of 200 mg m⁻³. At the same experimental conditions, almost 100% removal efficiency was achieved and the energy consumption was only 12.8 and 14.9 Wh m⁻³ by the series and parallel modes. In the case of 50 mg m⁻³ NH₃ removal at the same gas-flow rate, the removal efficiencies with the single mode, the series and parallel modes were 64, 92 and 70%, respectively. The energy requirement did not increase at the same residence time under the experimental conditions of the single mode with a gas-flow rate of 11.5 m³ h⁻¹ and the series or parallel mode with a gas-flow rate of 23.0 m³ h⁻¹. The experimental results indicate that the series and parallel modes are effective in saving energy consumption, improving removal ability and efficiency, especially for the series mode.