Exploring the reaction channels between arsine and the hydroxyl radical

The aim of this study was to present the reaction mechanism channels between arsine (AsH₃) and hydroxyl (OH) which was evaluated at CCSD(T)/CBS//CCSD/cc-pVTZ level. One potential channel is the hydrogen abstraction pathway (R1), leading to AsH₂ and H₂O products, which occurs due to the formation of an entrance complex (AsH₃OH) followed by a 1,2-hydrogen shift pathway (involving the proton transfer from the arsine group to hydroxyls, with one leading to the products). Additional channels are accessed via H-elimination pathways of the entrance complexes, forming arsinous acid (AsH₂OH; R2) and arsine oxide (AsH₃O; R3). In this respect, R2 is the only exoergic route of the three exit channels, representing the major branching ratio at 200–1000 K and, after 2000 K, R1 increases gradually becoming the major route of this reaction. In contrast, even at 4000 K, R3 is a highly unfeasible pathway. Therefore, the information predicted here provides new insights into the neutral–neutral chemical reaction dynamics regarding the Group V hydrides. On the other side, the R2 pathway may have some potential to solve the arsine oxidation puzzle as a possible primary pathway to the arsenic-oxygen species formation.     

Experimental equipment for studies of interaction of IR-radiation with liquid hydrides of groups IV–VI elements

The complex of special experimental apparatus for studies of interaction between IR-radiation and the thermally-stable volatile inorganic hydrides of groups IV–VI elements of the 2nd, 3rd and 4th periods in the liquid state and in the liquefied gas solutions is described. The main methods of solute concentration and integral absorption coefficients measurement are considered. The results of studies of IR-radiation absorption by volatile inorganic hydrides such as SiH₄, NH₃, PH₃, AsH₃, H₂S, and H₂Se in the liquid state and in the cryogenic solutions are presented. Using intensity, frequency and IR-absorption band contour data, the main mechanisms of intermolecular interactions in these liquids are discussed.     

Rotational Spectrum of the AsH(2) Radical in Its Ground State, Studied by Far-Infrared Laser Magnetic Resonance

The rotational spectrum of AsH₂ in its ground X̃²B₁ electronic state has been recorded using a far-infrared laser magnetic resonance spectrometer. The AsH₂ radical was produced inside the spectrometer cavity by the reaction of arsine (AsH₃) with fluorine atoms. Hyperfine splittings from both ⁷⁵As and ¹H nuclei were observed, and analysis of the spectra has yielded accurate values for rotational, hyperfine, and Zeeman parameters.     

Three-dimensional ab initio dipole moment surfaces and stretching vibrational band intensities of the XH3 molecules

Stretching vibrational band intensities of XH₃ (X=N, Sb) molecules are investigated employing three-dimensional dipole moment surfaces combined with the local mode Hamiltonian model.The dipole moment surfaces of NH₃ and SbH₃ are calculated with the density functional theory and at the correlated MP2 level,respectively. The calculated band intensities are in good agreement with the available experimental data. The contribution to the band intensities from the different terms in the polynomial expansion of the dipole moments of four group V hydrides (NH₃, PH₃,AsH₃ and SbH₃) are discussed. It is concluded that the breakdown of the bond dipole approximation must be considered. The intensity “borrowing” effect due to the wave function mixing among the stretching vibrational states is found to be less significant for the molecules that reach the local mode limit.     

Effects of growth conditions on the photoluminescence spectra of epitaxial GaAs films made by the hydride method

A study has been made of the effects of growth temperature and vapor-gas mixture composition in the diffusion region on the photoluminescence spectra at 77°K for GaAs films. It is shown that the growing film takes up an uncontrolled impurity whose level lies at a depth of 0.026 ±- 0.003 eV, which is determined by the ratio of the [AsH₃] concentration to [TMG] in the gas phase. In the range 560–670°C, this ratio is controlled by the degree of decomposition of the arsine, while at higher temperatures it is controlled by desorption of this from the surface.     

Spectral and luminescent investigations of ammonia cyclometalated Pt(II) complexes

A method of synthesis of ammonia cyclometalated Pt(II) complexes [Pt(NH₃)₂C∧N]ClO₄, where C∧N is 2-phenylpyridinate or 2-phenylbenzothiazole ion, is developed. The electronic absorption and emission properties of the complexes are studied. It is found that the state responsible for intense long-lived luminescence is the excited charge-transfer state of the ³(d-π*) type, the π* orbital being localized at the corresponding cyclometalating ligand. Formation of platinum blue is observed in air-saturated aqueous solutions of ammonia cyclometalated complexes.     

Interaction of PH3 coadsorbed with H2, D2, O2 and H2O on Rh(100)

The coadsorption of PH₃ with H₂, D₂, O₂ and H₂O on Rh(100) has been studied using temperature programmed desorption (TPD), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). The adsorption and molecular desorption of PH₃ is not affected by preadsorbed H₂, D₂ and O₂. Preadsorbed PH₃ blocks H₂ desorption sites while postdosed PH₃ displaces H₂ (D₂₁) from the Rh(100). When D₂ and PH₃ are coadsorbed, no D appears in desorbed phosphine. Preadsorbed O₂ reduces the amount of H₂ desorption (from PH₃ decomposition) and increases the H₂ desorption temperature. There is also some reaction between O(a) and H(a) to form water. Preexposure to H₂O decreases the extent of PH₃ adsorption and of PH₃ decomposition.     

MOCVD生长GaAs高质量掺碳研究

利用低压金属有机化合物汽相淀积(LP-MOCVD)系统,通过调节生长参量和掺杂工艺,得到了晶格质量高、表面形貌好且空穴浓度从8×10¹⁷到4×10²¹可控的掺碳GaAs外延层,最后给出一应用实例-用重掺碳的GaAs材料做级联GaInP/GaAs/Ge太阳能电池的隧道结.     

The study of microwave pressure lineshifts

The results of experimental investigations of pressure shifts and broadening of spectral lines of polar molecules performed in the submillimeter region by a microwave spectrometer RAD are reported. About 30 measurements were made of self-shift and foreign gas shift parameters of the lines of NH₃, PH₃, AsH₃, and H₂O molecules including lineshifts in excited vibrational states, lineshifts of transitions connected by common levels, lines with various values of J and K quantum numbers, and the “forbidden” |ΔK| = 3 lines. On the basis of the data obtained in this work and data available in the literature, new experimental dependences of lineshifts on molecular parameters are found. The results are well described by a simple “Stark effect” model of lineshifts. Some new directions of investigations are outlined.     

Submillimeter spectrum and spectroscopic constants of the arsine molecule in the ground vibrational state

The submillimeter spectrum of the arsine molecule, AsH₃, of both the allowed R-branch transitions (J + 1 ← J, J = 0, 1, 2, 3) and forbidden transitions of the Q branches, |K| = 4 ← 7, 5 ← 8, 6 ← 9, is investigated in the frequency range from 220 to 900 GHz. Weak absorption lines were observed by using the spectrometer RAD with sensitivity increased by a nontunable cavity cell. On the basis of the results obtained and microwave data available in the literature the rotational spectrum of the arsine molecule in the ground state is analyzed.     

Raman and IR spectra of crystalline phosphine in the γ phase

The γ phase of crystalline phosphine has been studied using IR and Raman spectroscopy. The observations include both pure phases, PH₃ and PD₃, and many of the modes of PH₃, PH₂D and PHD₂ dilute in PD₃ as well as of PD₃, PD₂H and PDH₃ dilute in PH₃. The phase transition β → γ is very slow for PH₃, but much more rapid for PD₃.Evidence is adduced pointing to the existence of inequivalent sites in this crystal, but none of a number of suggested models for the unit cell is entirely consistent with the numbers of multiplet components of the internal modes, nor with the numbers of external (lattice) modes observed in the IR and Raman.     

Formation of half-metallic MnAs and MnP layers

Half-metallic MnAs and MnP layers were grown on GaAs substrates by the laser sputtering of a metal Mn target in a hydrogen and arsine (phosphine) flow. The effect of the arsine concentration in the gascarrier and the substrate temperature (T _g = 300—450°C) on the crystal structure and electrical and magnetic properties were determined. It was shown that MnP samples grown at T _g ≥ 400°C exhibit ferromagnetic properties up to 300 K, according to Hall effect measurements.     

Extinction strain rates of premixed ammonia/hydrogen/nitrogen-air counterflow flames

Chemical energy vectors will play a crucial role in the transition of the global energy system, due to their essential advantages in storing energy in form of gaseous, liquid, or solid fuels. Ammonia (NH₃) has been identified as a highly promising candidate, as it is carbon-free, can be stored at moderate pressures, and already has a developed distribution infrastructure. As a fuel NH₃ has poor combustion properties that can be improved by the addition of hydrogen, which can be obtained energy-efficiently by partially cracking ammonia into hydrogen (H₂) and nitrogen (N₂) prior to the combustion process. The resulting NH₃/H₂/N₂ blend leads to significantly improved flame stability and resilience to strain-induced blow-out, despite similar laminar flame properties compared to equivalent methane/air flames. This study reports the first measurements of extinction strain rates, measured using the premixed twin-flame configuration in a laminar opposed jet burner, for two NH₃/H₂/N₂ blends over a range of equivalence ratios. Local strain rates are measured using particle tracking velocimetry (PTV) and are related to the inflow conditions, such that the local strain rate at the extinction point can be approximated. The results are compared with 1D-simulations using three recent kinetic mechanisms for ammonia oxidation. By relating the extinction strain rates to laminar flame properties of the unstretched flame, a comparison of the extinction behaviour of CH₄ and NH₃/H₂/N₂ blends can be made. For lean mixtures, NH₃/H₂/N₂-air flames show a significant higher extinction resistance in comparison to CH₄/air. In addition, a strong non-linear dependence between the resistance to extinction and equivalence ratio for NH₃/H₂/N₂ blends is observed.     

Investigation of the Fine Rotational Structure of the Fourth (500; A 1, E) Overtone of the AsH3 Molecule

The results of investigations into the high-resolution Fourier spectrum of the AsH₃ molecule first registered in the range 9720–9900 cm^–1 with a resolution of 0.015 cm^–1 are given in the present paper. Lines of (500; A ₁) and (500; E) bands are interpreted by the method of combination differences. The spectroscopic constants of the examined arsine bands are determined by solving the inverse problem. They have allowed 98 rotational energy levels (with J ^max = 6) to be reproduced with errors close to the experimental ones.     

Ultrafast dynamics in the excited hydrogen atom transfer states of ammonia clusters

Neutral ammonia clusters (NH₃)_m are photo-excited to the electronic state by a deep UV femtosecond laser pump pulse. Within a few hundred femtoseconds a significant fraction of the clusters rearrange to form an H-transfer state (NH₃)_m-2NH₄(3s)NH₂ with the subunit NH₄ in its 3s electronic ground state. This state is then electronically excited by a time-delayed infrared control pulse of variable wavelength. Finally, a third (probe) pulse in the UV ionizes the clusters for detection. The lifetime of the excited (NH₃)_m-2NH₄(3p)NH₂ states is found to vary between 2.7 and 0.13 ps depending on cluster size and excitation energy. It increases drastically upon deuteration. The corresponding cluster size-dependent photoelectron spectra allow us to disentangle the underlying energetics of the excitation and ionization process and reveal additional processes, such as nonresonant ionization or dissociative ionization. The experimental findings suggest that the excited H-transfer ammonia complexes with m > 2 are deactivated by an internal conversion process back to the electronically lowest H-transfer state followed by fast dissociation. Received 22 September 2001 and Received in final form 31 January 2002     

Singlet excited states of anions with higher main group elements

Previous studies have shown that dipole-bound excited states exist for certain small anions. However, valence excited states have been reported for some closed-shell anions, but those with singlet valence excited states have, thus far, contained a single silicon atom. This work uses high-level coupled cluster theory previously shown to reproduce excited state energies to better than 0.1 eV compared with experiment in order to examine the electronic excited state properties of anions containing silicon and other higher main group atoms as well as their first row analogues. Of the 14 anions involved in this study, 9 possess bound excited states of some kind: CH₂SN^?, C₃H^?, CCSiH^?, CCSH^?, CCNH^?₂, CCPH^?₂, BH₃PH^?₂, AlH₃NH^?₂ and AlH₃PH^?₂. Two possess clear valence states: CCSiH^? and its first row analogue C₃H^?. Substantial mixing appears to be present in the valence and dipole-bound characters for the first excited state wavefunctions of many of the systems reporting excited states, but the mixing is most pronounced with the ammonia borane-like AlH₃NH^?₂, and AlH₃PH^?₂ anions. Inclusion of second row atoms in anions whose corresponding radical is strongly dipolar increases the likelihood for the existence of excited states of any kind, but among the systems considered to date with this methodology, only the nature of group 14 atoms in small, closed-shell anions has yet been shown to allow valence singlet excited states.     

Lattice variation and thermal parameters of gel grown KDP crystals added with some ammonium compounds

Pure and impurity added (with NH₄Cl, NH₄NO₃, NH₄H₂PO₄, and (NH₄)₂SO₄) KDP single crystals were grown by the gel method using silica gels. X-ray diffraction data were collected for powder samples and used for the estimation of lattice variation and thermal parameters like Debye-Waller factor, mean-square amplitude of vibration, Debye temperature and Debye frequency. The thermal parameters do not vary in a particular order with respect to impurity concentration. The results obtained are reported and discussed.     

Far infrared spectrum and spectroscopic constants of AsH3 in the ground state

The far ir spectrum of arsine, AsH₃, was recorded in the range 25–100 cm^?1 with a resolution of approximately 0.004 cm^?1. ΔJ = +1, ΔK = 0 rotational transitions were measured and assigned up to J″ = 12. These transitions, together with the presently available microwave and submillimeter-wave data and ground state combination differences, were analyzed on the basis of a rotational Hamiltonian which includes Δk = ±3 and Δk = ±6 interaction terms. The derived ground state molecular parameters reproduced the transition frequencies of both allowed and “perturbation allowed” transitions within the accuracy of the measurements. The equilibrium structure was determined for the AsH₃ molecule.     

Ellipsometric studies of chemisorption on GaP(110) single crystals

Ellipsometry has been used to study the room temperature adsorption of H₂, O₂, Cl₂, Br₂, HCl, HBr, HI, H₂S, CH₃SH, H₂Se, NH₃, PH₃ and AsH₃ on GaP(110) surfaces; CO, CO₂ and CH₄ did not adsorb. Initial sticking coefficients were determined from the change in the ellipsometric angle Δ with time at a constant gas pressure and found to lie between I and 10 ^?5. The change in both Δ and ψ at monolayer coverage was measured as a function of wavelength in the visible and near UV for several gases. The observed structure was at variance with theoretical expectation for non-absorbing layers and, further, appeared similar for each adsorbate. This is attributed to small changes in the optical properties of the substrate arising from the removal of intrinsic surface states by chemisorption. Analysis of the data reveals GaP surface states with a maximum interband transition probability at a greater than band gap energy of 3.5eV. The optical constants of film-free GaP were also measured between 2 and 5.5eV, and direct interband transitions between bulk states were located at 3.76 and 5.05eV.     

Electron paramagnetic resonance studies of the alkaline earth hexaammines

Conduction electron paramagnetic resonance (CEPR) was investigated in Ca(NH₃)₆, Sr(NH₃)₆, and Ba(NH₃)₆ in the range 8.5 to 300 K. CEPR lineshapes in Ca(NH₃)₆ and Sr(NH₃)₆ are Dysonian, and by analyzing the lineshape the relaxation time, g shift, and diffusion time were determined. A line-broadening transition, which is associated with rapid ammonia diffusion, occurs below about 120 K in both compounds. However, no CEPR signals could be detected in Ba(NH₃)₆. In general, the results of this study indicate that the dominant relaxation mechanism involves the motional modulation of the spin-orbit coupling between the conduction electrons and cations. A narrow signal, which may be associated with local-moment formation, also was observed in Sr(NH₃)₆ below about 200 K.