On the response of LR-115 plastic track detector to 10 20 Ne-ion

The track etch rates of ₁₀ ²⁰ Ne-ion in cellulose nitrate (LR-115) have been measured for different temperatures and the activation energy is determined. The experimental results show that both the track etch rate and the normalized track etch rate depend on the energy loss as well as on etching temperature. The maximum etched track length of ₁₀ ²⁰ Ne-ion agrees with the theoretically computed range. The experimental results show that there is no sharp threshold, at least in CN(LR-115).     

Calibration of different plastic track detectors using accelerated heavy ions

Measurements of the dependence of track etch rate on the energy-loss of different ions have been presented. In this method, ₁₈ ⁴⁰ Ar, ₁₀ ²² Ne, ₈ ¹⁶ O and ₆ ¹² C-ions of different energies are used as energetic heavy ions for track formation in the detectors. The bulk etch rate and track etch rate are measured for different temperatures and hence the activation energies are determined. The variation ofV =V _t /V _b along the trajectory of the track has been shown for different temperatures. The maximum etched track length is compared with the theoretical range as well as with the range reported earlier. The experimental results indicate the absence of a well-defined threshold in the plastics studied.     

A modified REL track formation model and its application to registration of 1 GeV/n Au and U ions in polycarbonate

Identification of heavy ions recorded in track detectors requires the knowledge of the physical processes which take place in each of the three steps involved in ion registration: (i) energy deposition by the incident particle in the detector; (ii) track formation; and (iii) the identification method itself. The amount of energy deposited by the incident particle per unit path length (dE/dx) is usually calculated by means of the Bethe–Bloch formula, which is described in terms of the so-called close and distant collisions. The REL track formation model excludes the contribution of close collisions when calculating the fraction of dE/dx leading to track formation. The identification method relates REL to a measurable signal S in the detector, so that S=g(REL)^h where g and h are parameters to be obtained from calibration. In this work, we present a modified REL model in which the energy deposited by close collisions may contribute partially to track formation. This contribution is accounted for by means of a new coefficient κ, introduced in the modified REL expression, which can take values between 0 and 1. We estimate the value of κ from measurements of tracks originated in polycarbonate detectors by incident Au and U ions of energy from accelerator. The results are consistent with a small contribution (κ0.3) of close collisions.     

Oxygen (O6+) ion beam irradiation effects on etching parameter in lexan polymeric track detector

The polymer Lexan was irradiated to 80MeV O⁶⁺ ion beam using the 15UD pelletron at Inter University Accelerator Centre, New Delhi. The ion fluence ranging from 10¹¹ to 3 × 10¹² ions/cm² has been used to study the dose effects of irradiation on Lexan. By using the etching technique, it is observed that the bulk etch rate of the sample increases with increasing the ion influence, while the activation energy associated with it show a decreasing trend which can be explained on the basis of polymer degradation.      

Response of Makrofol polycarbonate plastic track detector to 1.1 MeV/N 54 132 Xe-ion

Makrofol polycarbonate plastic track detectors have been exposed to ₅₄ ¹³² Xe -ions of energy 1.1 MeV/N from the cyclotron beam. The bulk etch rate and track etch rate are measured for different temperatures and the activation energies are calculated. The maximum etched track length is compared with the theoretically computed range. The critical energy loss is (dE/dx) _c =5 MeV cm² mg⁻¹ for this detector material.     

Investigation of response of CR-39, PM-355 and PM-500 types of nuclear track detectors to energetic carbon ions

Samples of CR-39, PM-355, and PM-500 plastic detectors were irradiated with carbon ions of energy ranging from 0.9 MeV to 14.7 MeV. After the irradiation the detector samples were etched for a period from 2 hrs to 10 hrs. Dependence of track diameters on the ion energy values for different etching times, and dependence of V_T/V_B as a function of incident carbon-ion energy, are presented.     

Track revelation and optical properties of pentaerythritol tetrakis (allyl carbonate) plastic for application as nuclear track detector: effects of gamma radiations

The etching conditions of an indigenously prepared thin film of pentaerythritol tetrakis(allyl carbonate) (PETAC) were standardised for the use as a nuclear track detector. The optimum etching times in 6?N NaOH at 70°C for the appearance of fission and alpha tracks recorded in this detector from a ²⁵²Cf solid source were found to be 30 min and 1.50?h, respectively. The experimentally determined values for the bulk and track-etch rates for this detector in 6?N NaOH at 70°C were found to be 1.7?±?0.1 and 88.4?±?10.7?µm/h, respectively. From these results, the important track etching properties such as the critical angle of etching, the sensitivity and the fission track registration efficiency were calculated and compared with the commercially available detectors. The activation energy value for bulk etching calculated by applying Arrhenius equation to the bulk etch rates of the detector determined at different etching temperatures was found to be 0.86?±?0.02?eV. This compares very well with the value of about 1.0?eV reported for most commonly used track detectors. The effects of gamma irradiation on this new detector in the dose range of 200–1000?kGy have also been studied using bulk etch rate technique. The activation energy values for bulk etching calculated from bulk etch rates measurements at different temperatures were found to decrease with the increase in gamma dose indicating scission of the detector due to gamma irradiation. The optical band gap of this detector was also determined using UV–visible spectrometry and the value was found to be 4.37?±?0.05?eV.     

Geometries and electronic structures of the hydrogenated diamond (100) surface upon exposure to active ions: A first principles study

To elucidate the effects of physisorbed active ions on the geometries and electronic structures of hydrogenated diamond films, models of HCO⁻₃ , H₃O⁺, and OH⁻ ions physisorbed on hydrogenated diamond (100) surfaces were constructed. Density functional theory was used to calculate the geometries, adsorption energies, and partial density of states. The results showed that the geometries of the hydrogenated diamond (100) surfaces all changed to different degrees after ion adsorption. Among them, the H₃O⁺ ion affected the geometry of the hydrogenated diamond (100) surfaces the most. This is well consistent with the results of the calculated adsorption energies, which indicated that a strong electrostatic attraction occurs between the hydrogenated diamond (100) surface and H₃O⁺ ions. In addition, electrons transfer significantly from the hydrogenated diamond (100) surface to the adsorbed H₃O⁺ ion, which induces a downward shift in the HOMO and LUMO energy levels of the H₃O⁺ ion. However, for active ions like OH⁻ and HCO⁻₃ , no dramatic change appears for the electronic structures of the adsorbed ions.     

Hartree–Fock and density functional theory study of remote substituent effects on heterolytic Fe–N bond energies of p‐G‐C6H4NHFe(CO)2(η5‐C5H5) and p‐G‐C6H4N(COMe)Fe(CO)2(η5‐C5H5)

The nature and strength of metal–ligand bonds in organotransition‐metal complexes are crucial to the understanding of organometallic reactions and catalysis. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–N bond energies of para‐substituted anilinyldicarbonyl(η⁵‐cyclopentadienyl)iron [p‐G‐C₆H₄NH(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄NHFp (1), where G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂] and para‐substituted α‐acetylanilinyldicarbonyl(η⁵‐cyclopentadienyl)iron [p‐G‐C₆H₄N(COMe)(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄N(COMe)Fp (2)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_het(Fe–N)'s. The linear correlations [r = 0.98 (g, 1a), 0.93 (g, 2b)] between the substituent effects of heterolytic Fe–N bond energies [ΔΔH_het(Fe–N)'s] of series 1 and 2 and the differences of acidic dissociation constants (ΔpK_a) of N–H bonds of p‐G‐C₆H₄NH₂ and p‐G‐C₆H₄NH(COMe) imply that the governing structural factors for these bond scissions are similar. And the linear correlations [r = ?0.99 (g, 1c), ?0.92 (g, 2d)] between ΔΔH_het(Fe–N)'s and the substituent σ_p^? constants show that these correlations are in accordance with Hammett linear free energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–N)'s. ΔΔH_het(Fe–N)'s(1, 2) follow the captodative principle. ME_{α‐COMe, para‐G}s include the influences of the whole molecules. The correlation of ME_{α‐COMe, para‐G}s with σ_p^? is excellent. ME_{α‐COMe, para‐G}s rather than ΔΔH_het(Fe–N)'s in series 2 are more suitable indexes for the overall substituent effects on ΔH_het(Fe–N)'s(2). Insight from this work may help the design of more effective catalytic processes. Copyright © 2012 John Wiley & Sons, Ltd.     

Electronic properties of metallic bilayers deposited on Cu(1 1 1): A comparative study

The nature and the dispersion of the electronic collective excitations in different metal bilayers (Na, Ca, Ag) deposited onto the Cu(1 1 1) surface were investigated by angle-resolved electron energy loss spectroscopy. We found a nearly-flat behavior of the surface plasmon energy (absence of dispersion) in Ca and Ag bilayers, characterized by the presence of d electrons, in good agreement with theoretical predictions within the framework of the s-d polarization model. On the contrary, an initial negative dispersion was observed in the Na bilayer. The intensity of the surface plasmon was vanishing in the long-wavelength limit in all cases.     

Angular distribution measurements of Li(p,α)He reaction at 140 keV proton energy using nuclear track detectors

Angular distributions of a ⁶Li(p,α) ³He reaction were measured at six angles for 140 keV proton energy using nuclear track detectors (NTDs). The measurements were carried out over 60°–160° lab. angles in 20° increments using a scattering chamber of 80° beam line of the 350 kV accelerator. A semiconductor silicon surface barrier (SSB) detector was placed at +160° and was used as a monitor. The results have shown that the CR-39 detector has excellent capabilities to distinguish 1.4–2.7 MeV α+ ³He particles from the ⁶Li(p,α) ³He reaction and 8–9.4 MeV α-particles from the ⁷Li(p,α) ⁴He reaction through their track diameters. However, it was not possible to distinguish between the 2.3 MeV ³He ions and the 1.7 MeV ⁴He ions from the ⁶Li(p,α) ³He reaction from their track diameter measurements, but it was possible to differentiate between the two, from the darker contrast of the ³He particles caused by its deeper tracks as compared to those of ⁴He.     

A computational study of C?X (X = H,C, F,Cl) bond dissociation enthalpies (BDEs) in polyhalogenated methanes and ethanes

Bond dissociation enthalpies (BDEs) play a significant role in the photolysis of Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which lead to the depletion of stratospheric ozone. In this work, we estimate the performance of Density Functional Theory (DFT) methods in calculating BDEs of CFCs and HCFCs, and find that DFTs are unreliable for this system. The reasons for the unreliability of DFT methods in this system are also concluded. Furthermore, composite ab initio methods G3 and G3B3 are demonstrated to accurately estimate BDEs of polyhalogenated lower alkanes. Eighty two experimental values from Comprehensive Handbook of Chemical Bond Energies (2007, 2nd edition) are re‐evaluated. Eight of them are doubted as having a deviation exceeding 20.0 kJ/mol between the theoretical and experimental values. We also systematically predict the BDEs in polyhalogenated methanes and ethanes. A further study is conducted on their relationships of structures and properties. Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of N and O‐atoms and N2 (A) Metastable Molecule Densities in the Afterglows of N2‐H2, Ar‐N2‐H2 and Ar‐N2‐O2 Microwave Discharges

Early afterglows of N₂‐H₂, Ar‐N₂‐H₂ and Ar‐N₂‐O₂ flowing microwave discharges are characterized by optical emission spectroscopy. The N and O atoms and the N₂ (A) metastable molecule densities are determined by optical emission spectroscopy after calibration by NO titration for N and O‐atoms and measurements of NO and N₂ band intensities. If an uncertainty of 30% is estimated on N‐atomic density, an inaccuracy of one order of magnitude is obtained on the O and N₂ (A) densities. In N₂‐(0.05‐2.5%)H₂ and Ar‐(1‐50%)N₂‐(0.05‐2.5%) H₂ gas mixtures, the O‐atoms are coming from O₂ impurities in the discharge. Concentrations of N and O‐atoms and of N₂ (A) densities are compared to the ones obtained in Ar‐(5‐50%)N₂‐(0.2‐2.5%) O₂ gas mixtures in which a controlled amount of O₂ is added. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Reactions of Wheland complexes: base catalysis in re‐aromatization reaction of σ complexes obtained from 1,3,5‐tris(N,N‐dialkylamino)benzene and arenediazonium salts

The usual idea on the two‐steps mechanism of aromatic electrophilic substitution reactions is that the first step (the attack of the electrophilic reagent on the activated substrate) is rate limiting, while the driving force of the reaction is the fast proton departure to recover the resonance energy of the aromatic substrate. The now examined systems allow the formation of stable σ cationic complexes (Wheland intermediates) which may be investigated by simple procedures. Data here reported represent a clear and simple instance of a measurement of the rate of the proton abstraction from a Wheland intermediate and they indicate that this proton abstraction occurs by base catalysis in a rate determining step. Probably, this feature is more frequent than that usually conceived in the mechanism of electrophilic aromatic substitution reactions, because these reactions are often carried out in reaction mixtures containing large amounts of proton acceptor species which might mask the possible base catalysis. Copyright © 2007 John Wiley & Sons, Ltd.     

An experimental and theoretical study on the preparation of 4,4′‐methylene‐bis(N,N‐dimethylaniline) in ionic liquid

The reaction of N,N‐dimethylaniline with tetrachloromethane in ionic liquid was found to give 4,4′‐methylene‐bis (N,N‐dimethylaniline) in considerable yield. The ionic liquid was prepared from N,N‐dimethylaniline which is also the one of raw materials for the preparation of 4,4′‐methylene‐bis (N,N‐dimethylaniline), and acts as both solvent and catalyst in the reaction. Mild reaction conditions, enhanced rates, improved yields, and reagents' reactivity which is different from that in conventional organic solvents are the remarkable features observed in ionic liquids. In addition, the results of calculations are in good accordance with the experimental outcomes. Copyright © 2016 John Wiley & Sons, Ltd.     

密度泛函理论研究MN@H_2O (M=Ga,Ge, In,Sn, Sb; N=M,Al)团簇的特性

采用密度泛函理论的B3LYP, B3P86, B1B95, P3PW91和PBE1PBE方法结合SDD, LANL2DZ和CEP-121G基组计算了d~(10)组态二聚物MN(M=Ga, Ge, In, Sn和Sb; N=M和Al)的几何结构.采用B3P86/SDD进一步研究了MN@H_2O团簇的几何结构及吸附能.结果表明,水分子结合在二聚物M_2上时,对二聚物影响较大,对水分子自身影响较小.将M_2中Ga, Ge, In, Sn或Sb替换一个原子为Al时,水分子在GeAl和SnAl上的吸附能变化较大,而在GaAl, InAl和SbAl上吸附能变化较小.另外, H_2O吸附在Ga, Ge, In, Sn和Sb上时,与吸附在Al上时,吸附能的变化不大.     

Adsorption mode change from adlayer- to restructuring-type with increasing coverage, evidenced by structural determination of c(2 × 2)→(4 × 4)→(5 × 5) sequence formed on Ni(001) by Li deposition

We determined surface structures in a structural sequence c(2 × 2)→(4 × 4)→(5 × 5) formed on Ni(001) at 370 K with increasing Li coverage by a dynamical low-energy electron diffraction analysis. The (4 × 4) and (5 × 5) are complex surface-structures involving restructuring of substrate surface atoms, and are analogous to the previously determined (3 × 3) and (4 × 4) structures formed for Li/Cu(001). The c(2 × 2) at low coverages is a Li adlayer, so a change of the adsorption mode from adlayer- to restructuring-type is evidenced in the course of increasing coverage within a monolayer range.     

A DFT study on the (2 + 3) cycloaddition reactions of 2‐nitropropene‐1 with Z‐C,N‐diarylnitrones

B3LYP/6‐31G* calculations for competing (2 + 3)‐cycloaddition pathways for 2‐nitropropene‐1 (1) to Z‐C, N‐diarylnitrones ( 2a – e ) suggest a concerted reaction mechanism. However, the results point to the strongly asymmetric nature of transition complexes. Increasing polarity of the reaction environment and presence of electron‐donating substituents in the nitrone phenyl rings contribute to the higher asymmetry of these structures. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface chemistry of NO and NO2 on the Pt(1 1 0)-(1 × 2) surface: A comparative study

The surface chemistry of NO and NO₂ on clean and oxygen-precovered Pt(1 1 0)-(1 × 2) surfaces were investigated by means of high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). At room temperature, NO molecularly adsorbs on Pt(1 1 0), forming linear NO(a) and bridged NO(a). Coverage-dependent repulsive interactions within NO(a) drive the reversible transformation between linear and bridged NO(a). Some NO(a) decomposes upon heating, producing both N₂ and N₂O. For NO adsorption on the oxygen-precovered surface, repulsive interactions exist between precovered oxygen adatoms and NO(a), resulting in more NO(a) desorbing from the surface in the form of linear NO(a). Bridged NO(a) experiences stronger repulsive interactions with precovered oxygen than linear NO(a). The desorption activation energy of bridged NO(a) from oxygen-precovered Pt(1 1 0) is lower than that from clean Pt(1 1 0), but the desorption activation energy of linear NO(a) is not affected by the precovered oxygen. NO₂ decomposes on Pt(1 1 0)-(1 × 2) surface at room temperature. The resulted NO(a) (both linear NO(a) and bridged NO(a)) and O(a) repulsively interact each other. Comparing with NO/Pt(1 1 0), more NO(a) desorbs from NO₂/Pt(1 1 0) as linear NO(a), and both linear NO(a) and bridged NO(a) exhibit lower desorption activation energies. The reaction pathways of NO(a) on Pt(1 1 0), desorption or decomposition, are affected by their repulsive interactions with coexisting oxygen adatoms.     

Electron–phonon coupling and vibrational modes contributing to linear electro‐optic effect of the efficient NLO chromophore 4‐(N,N‐dimethylamino)‐N‐methyl‐4′‐toluene sulfonate (DAST) from their vibrational spectra

The optimized geometry and structural features of the most prospective electro‐optic crystal 4‐(N,N‐dimethylamino)‐N‐methyl‐4′‐toluene sulfonate (DAST), and the vibrational spectral investigations have been comprehensively described with the near infrared Fourier transform (NIR FT) Raman and Fourier transform infrared (FT‐IR) spectra supported by the density functional theoretical (DFT) computations to elucidate the contribution of vibrational modes to the linear electro‐optic (LEO) effect. Mulliken population analysis and natural bond orbital (NBO) analysis have also been carried out to analyze the effects of intramolecular charge transfer (ICT), intramolecular hydrogen bonding and hyperconjugative interactions on the geometries. The influence of CT interaction between the phenyl ring and the dimethylamino group of the nonlinear optical (NLO) chromophore on the endocyclic and exocyclic angles, and the electronic effects such as hyperconjugation and back‐donation on the methyl hydrogen atoms have been examined. The concurrent intense activation of Raman and IR activities of the effective conjugation vibrational coordinate, which significantly contributes to the LEO effect resulting from the strong electron–phonon (e/ph) coupling, has been analyzed in detail. The effects of frontier orbitals, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), transition of electron density (ED) transfer and the influence of planarity in the stilbazolium ring on the first hyperpolarizability are also discussed. Copyright © 2008 John Wiley & Sons, Ltd.