Electronegativities in the calculation of diatomic molecular parameters (Hydrides of some transition elements)

The force constants for diatomic molecules and isolated bonds may be expressed by using equalized electro-negativities, bond orders, bond strengths and interatomicdistances. We have studied Mn¹H, Mn²H, Co²H, Ni¹H, Ni²H, Cu¹H, Cu²H, Ag¹H, and Ag²H and have determined the proportionality constant d, as well as the Lennard-Jones parameters a and b, for the potential energy functions used by Szöke and calculated the anharmonicity ω_eξ_e and the rotational-vibrational coupling constant α_e. The relation between electronegativity and ionization potential has been verified and the variations of molecular parameters with atomic number Z have been studied.     

The infrared spectrum of the ν1 band of SiD3H

High-resolution spectra of the ν₁ stretching band of SiD₃H were recorded and analyzed, yielding values for ground- and upper-state constants and the band center. For ²⁸SiD₃H, B₀ = 1.777482(14) and ν₁ = 2187.2070(17) cm^?1. Similar analyses were performed on the less abundant species ²⁹SiD₃H and ³⁰SiD₃H.     

1H NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH₃)_xC₂₄ (x ∼ 4, M = K, Rb, Cs), three sets of triplet ¹H NMR spectral lines have been observed at various temperatures and orientations due to the ¹H-¹H and ¹⁴N-¹H dipolar interactions. We have inferred the structures of these compounds as mobile (liquid-like) intercalant layers of planar M(NH₃)₄ ions in the between the carbon layers. For the intercalated ammonia molecules, the potential barrier is ∼ 0.2 eV and the molecular geometry is very close to the free NH₃ in gas phase.     

Static H-2-H-2 Dipole Interactions in a Lyotropic Liquid-Crystal - A 2Dqe Study

The ²H NMR two-dimensional quadrupolar-echo spectra of an α-deuterated surfactant in an aligned hexagonal lyotropic liquid crystal were recorded. Whereas only indications of ²H-¹H and ²H-²H dipole splittings were observed in the F₂ spectra, these residual interactions were displayed in the F₁, spectra as an apparently Lorentzian peak. When gated ¹H decoupling was used, the ²H-²H dipole splittings became visible in the F₁ spectra as three (apparently Lorentzian) peaks. From a fit to the experimental lineshape the frequencies, relative amplitudes, line-widths, and phases of these peaks were determined. The ratio between the ²H-²H dipole and ²H quadrupole splittings was found to be |q| = 0.0041. Since q values of about −0.0040 have been obtained in lamellar phases, these results indicate that the α-methylene angular distribution function with respect to the local surface normal of the cylindrical aggregates may not deviate significantly from threefold symmetry.     

Proton diffusion in the room-temperature phase of [(NH4)1−xRbx]3H(SO4)2 as studied by 1H spin-lattice relaxation in the rotating frame

Proton diffusion in the room-temperature phase (phase II) of [(NH₄)_1?xRb_x]₃H(SO₄)₂ (0≤x≤1) has been studied by means of ¹H spin-lattice relaxation times in the rotating frame, T_1ρ. The ¹H T_1ρ values were measured at 200.13 MHz in the range of 380–490 K. The ammonium protons and the acidic protons have independent T_1ρ values in the higher temperature range of phase II, suggesting that the spin diffusion between the two species is ineffective. The translational diffusion of the acidic protons is the most dominant mechanism to relax both the ammonium protons and the acidic protons in phase II. The ¹H T_1ρ values in phase II are analyzed theoretically and the motional parameters are obtained. The results of NMR well explain the macroscopic proton conductivity.     

13C solid-state NMR chromatography by magic angle spinning 1H T1 relaxation ordered spectroscopy

An efficient method to separate the ¹³C NMR spectra of solid mixtures is introduced. The ¹H longitudinal (T₁) relaxation time is used to separate the overlapping ¹³C chemical shift spectra of solid mixtures via an inverse Laplace transform (ILT) of the relaxation dimension. The resulting 2D spectrum of the mixture contains separate ¹³C spectra for each component of the mixture that are identical to ¹³C spectra of the isolated materials. The separation is based on the equalization of ¹H T₁ values in a single domain by rapid ¹H spin diffusion and on the ¹H T₁ value differences between different domains. The introduction of a general ILT scheme enables efficient and reduced data acquisition time. The method is demonstrated on a mixture of two disaccharides and on a commercial drug containing several compounds.     

1H NMR study of the α phase of Mg2NiHx system

Hydrogen behavior in the α phase of Mg₂NiH_x system was studied by ¹H NMR. ¹H NMR spectra and spin-lattice relaxation times, T₁ and T_1ρ, of Mg₂NiH_0.22 were measured in the temperature range between 100 and 480 K. The drastic change in the linewidth is observed between 170 and 340 K, and ¹H rigid lattice is observed below 170 K, from which it is deduced that the hydrogen atoms are randomly distributed in α-Mg₂NiH_x. The relaxation mechanism for t₁ is the paramagnetic one, while the T_1ρ value is determined partially by hydrogen diffusion. The hydrogen diffusion rate has been determined from the linewidth and the T_1ρ value. The paramagnetic relaxations observed in T₁ and T_1ρ have been discussed relating to the hydrogen diffusion.     

Collision-induced dissociation of H 2 + ions into the fragmentations H+H(2p) and H++H(2p)

Using a photon-particle delayed coincidence method the energy distributions of H +H(2p) and H⁺+H(2p) fragment pairs have been measured arising from collisional dissociation of 10 keV H ₂ ⁺ ions incident on various target gases. H fragments in their 2p state are identified by the Lymanα radiation emitted. The distribution of H+H(2p) fragment pairs arising from dissociative charge exchange reveals a sharp increase below 0.2 eV in the center-of-mass frame of the H ₂ ⁺ ion. This is ascribed to predissociation of vibrational levels of higher H₂ Rydberg states close above then=2 dissociation limit by those H₂ Rydberg states which separate into H+H(2p) fragments. Only direct transitions into the continuum of theGK ¹ ∑ _g ⁺ state may compete. Some structure at 0.3–0.5 eV is attributed to the three statesI ¹ П _g,i ³ П _g, andh ³ bE _g ⁺ having potential barriers of this height. The distributions for H⁺+H(2p) have maxima at 3.4, 3.8, and 4.2 eV for a H₂, Ar, and He target, respectively, indicating that the 2pπ _u state as well as the 3dσ _g state ofH ₂ ⁺ is excited. The H+H(2p) process has a greater probability than the H⁺+H(2p) process for Ar and H₂ targets, though all electronic H₂ states under consideration are bound.     

Ionization of hydrogen and deuterium atoms in thermal energy collisions with state-selected Ne(3s 3 P 2,3 P 0) metastable atoms

High resolution energy spectra of electrons and ions resulting from thermal energy collisions of hydrogen and deuterium atoms with state-selected metastable Ne(Ne(3s ³ P ₂,³ P ₀) atoms are reported. The electron spectra for Ne(³ P ₂)+H(D) are very broad: The high energy part due to formation of NeH⁺ (NeD⁺) bound states (associative ionization), amounts to about 30% of the ionizing events, whereas the dominant part of the spectrum including a prominent low-energy peak is due to Penning ionization out of a strongly-attractive entrance potential curve. Comparison of the spectra with quantum mechanical fit calculations yields fairly accurate information on this potential, in particular its well depthD _e [Ne(³ P ₂)?H,D]= 2.0(1) eV. The spectra for Ne(³ P ₀)+H, D are comparatively narrow with much lower cross sections than the one for the Ne(³ P ₂) state. The corresponding entrance channel is a weakly bound van der Waals molecule with a well depth below 0.1 eV. A perturbation calculation of the Ne(3s)+H(1s) potential energy curves at large distances explains the observed difference between the Ne(³ P ₂)+H(D) and Ne(³ P ₀)+H(D) systems. Symmetry arguments are given that the major contribution to the Ne(³ P ₂)+H(D) spectra is due to the² Σ potential.     

Bonding and composition diagrams for sputtered a-Si : H

The combined influence of H partial pressure (p_H) and deposition rate (R_D) on Si-H bonding and total H content in diode-sputtered a-Si : H is presented in two simple graphs for the case of substrate temperature (T_s) equal to 225°C. Similar to a phase diagram, the graphs predict the H content and Si-H bonding that will result if a deposition is carried out with any prescribed pair of values (p_H, R_D), where 0.04 < p_H < 10 Paand 0.01 < R_D < 1 nm/sec. Well defined regions of Si-H bonding represented by dominant infrared stretching absorptions at 2000, 2090 and 2150 cm^?1 are obvious in the bonding diagram. The absorption at 2090 cm^?1 is the most commonly observed and is obtainable over a wide range of intermediate values of p_H and R_D. The absorption at 2000 cm^?1 is dominant only for the lowest p_H and the highest R_D. The absorption at 2150 cm^?1 is dominant in films deposited at high p_H and low R_D. The composition diagram shows that highest total H content is obtained for low R_D and high p_H, and lowest total H content results for high R_D and low p_H     

Proton magnetic resonance study of the phase transitions of [N(CH3)4]2BCl4 (B=Co, Cu, Zn, and Cd) single crystals

The proton spin-lattice relaxation rates in [N(CH₃)₄]₂BCl₄ (B=⁵⁹Co, ⁶³Cu, ⁶⁷Zn, and ¹¹³Cd) single crystals grown using the slow evaporation method were investigated over the temperature range 120-400 K. It was found that the relaxation processes of ¹H for all the [N(CH₃)₄]₂BCl₄ crystals can be described with single exponential functions. The changes in the ¹H relaxation behavior in the neighborhood of the phase transition temperatures are used to detect changes in the state of internal motion. From the ¹H spin-lattice relaxation rate measurements for [N(CH₃)₄]₂BCl₄ crystals, the activation energies were calculated for each phase. The large values of the activation energies indicate that the N(CH₃)₄ groups are significantly affected during the transitions. Although these [N(CH₃)₄]₂BCl₄ crystals all belong to the group of A₂BX₄-type crystals, their ¹H spin-lattice relaxation rates have different temperature dependences and indicate the occurrence of different molecular motions within the crystals. We additionally show for the first time that the differences in ¹H spin-lattice relaxation rates among the [N(CH₃)₄]₂BCl₄ (B=⁵⁹Co, ⁶³Cu, ⁶⁷Zn, and ¹¹³Cd) single crystals arise from differences in the electron structures of the metal ions within the series.     

H and K spin-lattice relaxation, ionic motion and Raman processes in the proton conducting KHSeO4 single crystal

The spin-lattice relaxation rates of ¹H and ³⁹K nuclei in KHSeO₄ crystals were studied in the temperature range 160-400 K. The spin-lattice relaxation recovery of ¹H nucleus in this crystal can be represented with a single exponential function, and the relaxation T₁⁻¹ curve of ¹H can be represented with the Bloembergen-Purcell-Pound (BPP) function. The relaxation process of ³⁹K with dominant quadrupole relaxation can be described by a linear combination of two exponential functions. T₁⁻¹ for the ³⁹K nucleus was found to have a very strong temperature dependence, T₁⁻¹=βT⁷. Rapid variations in relaxation rates are associated with critical fluctuations in the electronic spin system. The T⁷ temperature dependence of the Raman relaxation rate is shown here to be due to phonon-magnon coupling.     

Diffusion of hydrogen and deuterium on the (111) plane of tungsten

The diffusion of ¹H and ²H on the (111) plane of a W field emitter has been studied by the fluctuation method at various coverages. Both activated and unactivated diffusion is observed; the latter shows very little isotope effect, suggesting that coupling to the substrate is so strong that mass renormalization makes the effective masses of ¹H and ²H nearly identical. Values of D in the tunneling, i.e. temperature independent, regime are 10^?13?5 × 10^?14 cm²/s depending on coverage. For activated diffusion at high coverages, corresponding to population of the β₁ state E = 2.4?3.2 kcal/mol and D₀ = 2 × 10^?8 ?5 × 10^?7 cm²/s, depending on coverage. For lower coverages, corresponding to β₂ population, E = 7–9 kcal/mol, D₀ = 9 × 10^?6 ?2 × 10^?3 cm²/s, again depending on coverage. Similar values are obtained for ²H, with E and D₀ values slightly reduced. An exponentially decaying correlation signal for clean W was also seen and interpreted in terms of flip-flop of W atoms.     

Structural Phase Transition of Perovskite-Type N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>CdBr<Subscript>3</Subscript> Studied by MAS NMR and Static NMR

The structural geometry change in the perovskite-type N(CH₃)₄CdBr₃ single crystal near the phase transition temperature of T _C = 390 K was investigated using magic angle spinning nuclear magnetic resonance techniques. For ¹H and ¹³C nuclei, the temperature dependences of their chemical shift, spectral intensity, and spin–lattice relaxation time (T _1ρ) in the rotating frame were obtained and analyzed. While the chemical shift and T _1ρ of ¹H showed change near T _C, those of ¹³C did not. In addition, the ¹¹³Cd spin–lattice relaxation time T ₁ in the laboratory frame near T _C show no evidence of anomalous change near the phase transition temperature, which coincides with the measured changes in the ¹H T _1ρ. The driving force for this phase transition was connected to the ¹H in the CH₃ groups.     

Rigid lattice NMR spectra of proton conductors H(H2O)nSbO3

The “rigid lattice” ¹H NMR spectra of H(H₂O)_nSbO₃ have been interpreted for n=0.20, 0.92 and 1. For n?0.92 the compounds contain deformed H₃O⁺ ions and OH groups. For n=1 the real formula is (H₃O)_0.7H_0.3SbO₃,0.3 H₂O. The results are discussed in relation to the level of proton conductivity.     

NMR study of re-entrant spin-glass state in NiMn alloys

The temperature dependence of the average hyperfine field H̄_i and the nuclear spin-lattice relaxation time T₁ of ⁵⁵Mn on three different types (i = I, II and III) of Mn atoms in NiMn alloys containing 10 and 15 at % Mn have been measured. In 15 at % Mn alloy, H̄_III associated with Mn atoms having an antiparallel moment μ_III increases abruptly at 12K, while H̄_I and H̄_II associated with Mn atoms having parallel moments μ_I and μ_II do not with decreasing temperature. On the other hand T⁻¹₁ of ⁵⁵Mn of all three types of Mn atoms are largely enhanced at the same temperature, 12 K. This behavior was not observed in 10 at % Mn alloy.These effects observed in 15 at % Mn alloy are considered to be due to the freezing of the transverse component of the antiparallel moment μ_III due to the onset of the re-entrant spin-glass transition at 12 K.     

Resonance states of hydrogen nuclei 4H and 5H obtained in transfer reactions with exotic beams

To investigate ⁵H resonance states with a better instrumental resolution, we utilized the two-neutron transfer reaction ³H(t, p)⁵H accomplished with the use of a cryogenic liquid-tritium target and 57.5-MeV triton beam. As a result of this study, a valuable fraction of protons detected at ? _lab=18°–32° in ptn coincidence events was attributed to the states of the ⁵H nucleus. Two resonance states situated at 1.8±0.1 and 2.7±0.1 MeV above the t + n + n decay threshold were obtained in the missing mass energy spectrum of the ⁵H nucleus. The peak located close to E5_H was clearly seen in the ⁵H spectrum obtained from the energy distributions of ³H nuclei emitted in the reaction ²H(⁶He, ⁵H)³He at ? _lab=17°–32°. The width (Γ_obs≤0.5 MeV) obtained for the two ⁵H resonance states is surprisingly small. A state of ⁴H with E _res=3.3 MeV and γ ²=2.3 MeV was obtained in the reaction ²H(t, p)⁴H from the spectra of protons leaving the target at ? _lab=18°–32° and detected in coincidence with neutrons emitted in the decay of ⁴H nuclei.     

TEOS-based low-pressure chemical vapor deposition for gate oxides in 4H–SiC MOSFETs using nitric oxide post-deposition annealing

The use of SiO₂/4H–SiC metal-oxide-semiconductor field-effect transistors (MOSFETs) can be problematic due to high interface state density (D_it) and low field-effect mobility (μ_fe). Here, we present a tetra-ethyl-ortho-silicate (TEOS)-based low-pressure chemical vapor deposition (LPCVD) method for fabricating the gate oxide of 4H–SiC MOSFETs using nitric oxide post-deposition annealing. SiO₂/4H–SiC MOS capacitors and MOSFETs were fabricated using conventional wet and TEOS oxides. The measured effective oxide charge density (Q_eff) and D_it of the TEOS-based LPCVD SiO₂/4H–SiC MOS capacitor with nitridation were 4.27 × 10¹¹ cm⁻² and 2.99 × 10¹¹ cm⁻²eV⁻¹, respectively. We propose that the oxide breakdown field and barrier height were dependent on the effective Q_eff. The measured μ_fe values of the SiO₂/4H–SiC MOSFETs with wet and TEOS oxides after nitridation were, respectively, 11.0 and 17.8 cm²/V due to the stable nitrided interface between SiO₂ and 4H–SiC. The proposed gate stack is suitable for 4H–SiC power MOSFETs.     

A study of molecular motion and Raman processes in K3H(SO4)2 and KHSO4 single crystals by observation of H and K spin-lattice relaxation

The spin-lattice relaxation rates for ¹H and ³⁹K nuclei in K₃H(SO₄)₂ and KHSO₄ single crystals, which are potential candidate materials for use in fuel cells, were determined as a function of temperature. The spin-lattice relaxation recovery of ¹H can be represented for both crystals with a single exponential function, but cannot be represented by the Bloembergen-Purcell-Pound (BPP) function, so is not related to HSO₄ motion. The recovery traces of ³⁹K, which predominantly undergoes quadrupole relaxation, can be represented by a linear combination of two exponential functions. The temperature dependences of the relaxation rates for ³⁹K can be described with a simple power law T₁⁻¹=αT². The spin-lattice relaxation rates for the ³⁹K nucleus in K₃H(SO₄)₂ and KHSO₄ crystals are in accordance with a Raman process dominated by a phonon mechanism.     

The formation of the superheavy hydrogen isotope <Superscript>6</Superscript>H in the absorption of stopped π<Superscript>−</Superscript>-mesons by nuclei

An experimental search for the superheavy hydrogen isotope ⁶H was conducted through studying the absorption of stopped π^?-mesons by ⁹Be and ¹¹B nuclei. A structure in the missing mass spectrum caused by the resonance states of ⁶H was observed in three reaction channels, namely, ⁹Be(π^?, pd)X, ¹¹B(π^?, d³He)X, and ¹¹B(π^?, p⁴He)X. The parameters of the lowest state E_r=6.6±0.7 MeV and Γ=5.5±2.0 MeV (E_r is the resonance energy with respect to the disintegration into the triton and three neutrons) are evidence that ⁶H is a more weakly bound system than ⁴H and ⁵H. Three excited states of ⁶H were observed. Their resonance levels (E_1r=10.7±0.7 MeV, Γ_1r=4±2 MeV, E_2r=15.3±0.7 MeV, Γ _2r=3±2 MeV, and E_3r=21.3±0.4 MeV, Γ_3r=3.5±1.0 MeV) are energetically capable of disintegrating into six free nucleons.