The Matrix Isolation Spectrum of the CH2 Ion

For CH₂⁺ molecular ions at 5 K we simulate the infrared absorption spectrum, and tabulate all strong absorption lines from 0 to 16 000 cm⁻¹. We use ab initio potential energy, dipole moment, and transition moment surfaces in conjunction with our program system RENNER, which allows for the Renner-Teller effect and spin-orbit coupling in a full-dimensions calculation. This is done for the purpose of guiding our search for the matrix isolation spectrum; our attempts at finding this spectrum are also described.     

The AB2-XA1 electronic transition of NO2: A rovibronic survey covering 14 300-18 000 cm

More than 250 rotationally resolved vibrational bands of the A²B₂-X²A₁ electronic transition of ¹⁵NO₂ have been observed in the 14 300-18 000 cm⁻¹ range. The bands have been recorded in a recently constructed setup designed for high resolution spectroscopy of jet cooled molecules by combining time gated fluorescence spectroscopy and molecular beam techniques. The majority of the observed bands has been rotationally assigned and can be identified as transitions starting from the vibrational ground state or from vibrationally excited (hot band) states. An exceptionally strong band is located at 14 851 cm⁻¹ and studied in more detail as a typical benchmark transition to monitor ¹⁵NO₂ in atmospheric remote sensing experiments. Standard rotational fit routines provide band origins, rotational and spin rotation constants. A subset of 177 vibronic levels of ²B₂ vibronic symmetry has been analyzed in the energy range between 14 300 and 17 250 cm⁻¹, in terms of integrated density and using Next Neighbor Distribution. It is found that the overall statistical properties and polyad structure of ¹⁵NO₂ are comparable to those of ¹⁴NO₂ but that the internal structures of the polyads are completely different. This is a direct consequence of the X²A₁-A²B₂ vibronic mixing.     

Study of the electron paramagnetic resonance spectra of Zn(antipyrine)2(NO3)2:VO

In this work, a full ligand-field energy matrix (10×10) diagonalization treatment for 3d¹ ions in tetragonal symmetry is developed on the basis of the two-s.o.-coupling-parameter model. Spin Hamiltonian parameters (g factors g_∥, g_⊥ and hyperfine structure constants A_∥, A_⊥) of the tetragonal V⁴⁺ center in Zn(antipyrine)₂(NO₃)₂ are calculated from the complete energy matrix diagonalization method and the perturbation theory method. The calculated results from both methods are not only close to each other but also in good agreement with the experimental values. Furthermore, the compressed defect structure of V⁴⁺ center is discussed.     

High-resolution study of the ν1 + ν2 and ν2 + ν3 strongly interacting bands of D2Se

A high-resolution Fourier transform spectrum of the D₂^MSe species (M = 82, 80, 78, 77, and 76) in the region 2300-2500 cm⁻¹ was recorded for the first time and assigned. On the basis of these experimental data, rotation-vibration energies of the (1 1 0) and (0 1 1) vibrational states were fitted, and band centers, and rotational, centrifugal distortion, and resonance interaction parameters were determined for the main D₂⁸⁰Se species. The obtained set of 32 fitted parameters reproduces the 647 rotation-vibration energies with a rms deviation of 0.00024 cm⁻¹. The ν₁ + ν₂ and ν₂ + ν₃ bands of the other four isotopic species are analyzed as well.     

Studies of the electrochemical reduction processes of Bi, HTeO2 and their mixtures

The reduction process of Bi³⁺, HTeO₂⁺ and their mixtures on Au electrode surface was studied by cyclic voltammetry, linear sweep voltammetry, electrochemical impedance spectroscopy and chronoamperometry. XRD and EDS methods were also used to measure the reductive products prepared under different potentials and provide the evidences of the reactions. The results indicate that the reduction of HTeO₂⁺ occurs at more positive potential than that of Bi³⁺, but its reduction rate is slower and adsorption phenomenon exists during its reduction process. Bi₂Te₃ compound can be obtained potentiostatically at a proper potential in all the mixed solutions with concentration ratio CHTe+O₂/CBi3+ in our research range (0.1-10). But pure Bi₂Te₃ compound can only be obtained at 42 mV in the solution with concentration ratio CHTe+O₂/CBi3+ equaling to 1. And the formation of Bi₂Te₃ compound is an inductive co-depositing process: (1) HTeO₂⁺ + 4e⁻ + 3H⁺ → Te⁰ + 2H₂O, (2) 3Te⁰ + 2Bi³⁺ + 6e⁻ → Bi₂Te₃.     

Highly excited,normally inaccessible vibrational levels by sub-doppler modulated gain spectroscopy: The Na2 A1Σ+u state

Modulated gain spectroscopy is a sensitive, widely applicable, rovibronically state selective, sub-Doppler, triple resonance method for examining excited vibronic levels which are Franck—Condon inaccessible from thermally populated levels of the electronic ground state. A cw optically pumped molecular laser (OPL) prepares a steady-state population in a selected, vibrationally highly excited, rotation-vibration level of the electronic ground state (the lower level of the OPL transition). An intensity-modulated, single frequency dye laser excites part of this intracavity OPL-prepared population to the level of interest, thereby causing an increase in the OPL population inversion density, and, in turn, its output power. As the frequency of the dye laser is scanned, resonances are selectively detected by the appearance of modulation on the OPL output power; discrimination against dye laser excitations out of levels unconnected with the OPL is nearly perfect. Sub-Doppler (≈300 MHz FWHM) transitions are observed, thereby extending knowledge of the Na₂A¹Σ⁺_u state from v=44 to 62.     

Enhanced photoluminescence properties of Zn2SiO4:Mn co-activated with Y/Li under VUV excitation

A series of green phosphors Zn_1.92−2xY_xLi_xSiO₄:0.08Mn²⁺ (0≤x≤0.03) were prepared by solid-state synthesis method. Phase and lattice parameters of the synthesized phosphors were characterized by powder X-ray diffractometer (XRD) and the co-doped effects of Y³⁺/Li⁺ upon emission intensity and decay time were investigated under 147 nm excitation. The results indicate that the co-doping of Y³⁺/Li⁺ has favorable influence on the photoluminescence properties of Zn₂SiO₄:Mn²⁺, and the optimal photoluminescence intensity of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 103% of that of commercial phosphor when the doping concentration of Y³⁺/Li⁺ is 0.01 mol. Additionally, the decay time of phosphor is much shortened and the decay time of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 3.39 ms, shorter by 1.83 ms than that of commercial product after Y³⁺/Li⁺ co-doping.     

Theoretical study on the kinetics for OH reactions with CH3OH and C2H5OH

Kinetics and mechanisms for reactions of OH with methanol and ethanol have been investigated at the CCSD(T)/6-311 + G(3df, 2p)//MP2/6-311 + G(3df, 2p) level of theory. The total and individual rate constants, and product branching ratios for the reactions have been computed in the temperature range 200-3000 K with variational transition state theory by including the effects of multiple reflections above the wells of their pre-reaction complexes, quantum-mechanical tunneling and hindered internal rotations. The predicted results can be represented by the expressions k₁ = 4.65 × 10⁻²⁰ × T^2.68 exp(414/T) and k₂ = 9.11 × 10⁻²⁰ × T^2.58 exp(748/T) cm³ molecule⁻¹ s⁻¹ for the CH₃OH and C₂H₅OH reactions, respectively. These results are in reasonable agreements with available experimental data except that of OH + C₂H₅OH in the high temperature range. The former reaction produces 96-89% of the H₂O + CH₂OH products, whereas the latter process produces 98-70% of H₂O + CH₃CHOH and 2-21% of the H₂O + CH₂CH₂OH products in the temperature range computed (200-3000 K).     

Rotational analysis of the (4, 8) band in the A-X system of Cl2

Thirty-four rovibronic spectral lines of the Ω=1/2 component of the (4, 8) band in the A-X system of ³⁵Cl₂⁺ were observed in the range of 16,940-17,010 cm⁻¹, employing optical heterodyne-enhanced velocity modulation spectroscopy. Nonlinear least-squares fitting the effective Hamiltonians results in precise band origin and other molecular constants of the levels involved.     

AsO+同位素离子X2∑+和A2∏电子态的多参考组态相互作用方法研究

采用包含Davidson修正多参考组态相互作用(MRCI)方法结合价态范围内的最大相关一致基As/aug-cc-pV5Z和O/aug-cc-pV6Z, 计算了AsO⁺ (X²∑⁺)和AsO⁺(A²∏)的势能曲线. 利用AsO⁺离子的势能曲线在同位素质量修正的基础上, 拟合出了同位素离子⁷⁵As¹⁶O⁺和⁷⁵As¹⁸O⁺的两个电子态光谱常数. 对于X²∑⁺态的主要同位素离子⁷⁵As¹⁶O⁺, 其光谱常数R_e, ω_e, ω_ex_e, B_e和α_e分别为 0.15770 nm, 1091.07 cm^-1, 5.02017 cm^-1, 0.514826 cm^-1和0.003123 cm^-1; 对于A²∏态的主要同位素离子⁷⁵As¹⁶O⁺, 其T_e, R_e, ω_e, ω_ex_e, B_e和α_e分别为5.248 eV, 0.16982 nm, 776.848 cm^-1, 6.71941 cm^-1, 0.443385 cm^-1和0.003948 cm^-1. 这些数据与已有的实验结果均符合很好. 通过求解核运动的径向薛定谔方程, 找到了J=0时AsO⁺(X²∑⁺)和AsO⁺(A²∏)的前20个振动态. 对于每一振动态, 还分别计算了它的振动能级、转动惯量及离心畸变常数, 并进行了同位素质量修正, 得到各同位素离子的分子常数. 这些结果与已有的实验值非常一致. 本文对于同位素离子⁷⁵As¹⁶O⁺(X¹∑⁺), ⁷⁵As¹⁸O⁺(X¹∑⁺), ⁷⁵As¹⁶O⁺(A¹∏)和⁷⁵As¹⁶O⁺(A¹∏)的光谱常数和分子常数属首次报导.     

Emission features of Ho ion in Nb2O5, Ta2O5 and La2O3 mixed Li2O-ZrO2-SiO2 glasses

Li₂O-ZrO₂-SiO₂: Ho³⁺ glasses mixed with three interesting d-block elemental oxides, viz., Nb₂O₅, Ta₂O₅ and La₂O₃, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb₂O₅ and Ta₂O₅ mixed Li₂O-ZrO₂-SiO₂ glasses (free of Ho³⁺ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta⁵⁺ and Nb⁵⁺ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho³⁺ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β_r and the radiative lifetime τ_r, for ⁵S₂ emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for ⁵S₂ level of Ho³⁺ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La₂O₃ mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho³⁺ ions.     

Reasons for the deactivation of Pt/TiO2 photocatalyst treated by inert gas N2

The effect of N₂ treatment on the photocatalytic activity of Pt⁰/TiO₂ was investigated. The results showed that after treatment at 500 °C in N₂, 70% of the photocatalytic activity of 1.0 wt.% Pt⁰/TiO₂ was lost by the evaluation of photocatalytic oxidation reaction of C₃H₆. Transmission electron microscopy (TEM) and Ar⁺ ion sputtering tests revealed that in the course of high-temperature N₂ treatment, the size of Pt⁰ particles on TiO₂ increases and a strong interaction between metal and support, i.e. Pt⁰ particles encapsulated by Ti_xO_y, happens, which are the reasons for the deactivation of Pt⁰/TiO₂ photocatalyst treated by high-temperature N₂.     

Rotationally resolved electronic spectroscopy of a nonlinear carbon chain radical C6H4

Rotationally resolved electronic spectrum of the origin band in the 2A″-X2A″ transition of a nonlinear carbon chain radical C₆H₄⁺ has been recorded in the 604 nm region using cw cavity ring down spectroscopy. The radical was produced by a discharge through an acetylene-helium mixture in a supersonic planar expansion. The rotational structure has been analysed and precisely determined. A band having a-type prolate rotational structure has also been observed near 581 nm. By considering the results of ab initio calculations this band is assigned to a transition involving the excitation of the ν₁₂ fundamental in the upper 2A″ electronic state of the same C₆H₄⁺ isomer.     

Enhanced luminescence of Ca3B2O6:Dy phosphors by Na-codoping for LED applications

The Ca_2.95−yDy_0.05B₂O₆:yNa⁺ (0≤y≤0.20) phosphors were synthesized at 1100 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence excitation (PLE), photoluminescence (PL) spectra and thermoluminescence (TL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid-state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions on 350 nm excitation was observed at 480 nm (blue) due to the ⁴F_9/2→⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2→⁶H_13/2 transitions and 660 nm (red) due to weak ⁴F_9/2→⁶H_11/2 emissions. The PL results from the investigated Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors show that Dy³⁺ emissions increase with the increase of the Na⁺ codoping ions. The integral intensity of yellow to blue (Y/B) can be tuned by controlling Na⁺ content. By the simulation of white light, the optimal CIE value (0.328, 0.334) can be achieved when the content of Na⁺-codoping ions is y=0.2. The results imply that the Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors could be potentially used as white LEDs.     

Ab initio chemical kinetics for the reactions of HNCN with O(P) and O2

The kinetics and mechanisms of the reactions of cyanomidyl radical (HNCN) with oxygen atoms and molecules have been investigated by ab initio calculations with rate constant prediction. The doublet and quartet state potential energy surfaces (PESs) of the two reactions have been calculated by single-point calculations at the CCSD(T)/6-311+G(3df, 2p) level based on geometries optimized at the CCSD/6-311++G(d, p) level. The rate constants for various product channels of the two reactions in the temperature range of 300-3000 K are predicted by variational transition state and RRKM theories. The predicted total rate constants of the O(³P) + HNCN reaction at 760 Torr Ar pressure can be represented by the expressions k_total (O + HNCN) = 3.12 × 10⁻¹⁰ × T^−0.05 exp (−37/T) cm³ molecule⁻¹ s⁻¹ at T = 300-3000 K. The branching ratios of primary channels of the O(³P) + HNCN are predicted: k₁ for producing the NO + CNH accounts for 0.72-0.64, k₂ + k₉ for producing the ³NH + NCO accounts for 0.27-0.32, and k₆ for producing the CN + HNO accounts for 0.01-0.07 in the temperature range studied. Meanwhile, the predicted total rate constants of the O₂ + HNCN reaction at 760 Torr Ar pressure can be represented by the expression, k_total(O₂ + HNCN) = 2.10 × 10⁻¹⁶ × T^1.28exp (−12200/T) cm³ molecule⁻¹ s⁻¹ at T = 300-3000 K. The predicted branching ratio for k₁₁ + k₁₃ producing HO₂ + ³NCN as the primary products accounts for 0.98-1.00 in the temperature range studied.     

Optical properties of Mn-activated Na2SnF6 and Cs2SnF6 red phosphors

Alkaline hexafluorostantanate red phosphors Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺ are synthesized by chemical reaction in HF/NaMnO₄ (CsMnO₄)/H₂O₂/H₂O mixed solutions immersed with tin metal. X-ray diffraction patterns suggest that the synthesized phosphors have a tetragonal symmetry with the space group D_4h¹⁴ (Na₂SnF₆:Mn⁴⁺) and a trigonal symmetry with the space group D_3d³ (Cs₂SnF₆:Mn⁴⁺). Photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and the Raman scattering techniques are used to investigate the optical properties of the phosphors. The Franck-Condon analysis of the PLE data yields the Mn⁴⁺-related optical transitions to occur at ∼2.39 and ∼2.38 eV (⁴A_2g→⁴T_2g) and at ∼2.83 and ∼2.76 eV (⁴A_2g→⁴T_1g) for Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺, respectively. The crystal field parameters (Dq) of the Mn⁴⁺ ions in the Na₂SnF₆ and Cs₂SnF₆ hosts are determined to be ∼1930 and ∼1920 cm⁻¹, respectively. Temperature-dependent PL measurements are performed from 20 to 440 K in steps of 10 K, and the obtained results are interpreted by taking into account the Bose-Einstein occupation factor. Comprehensive discussion is given on the phosphorescent properties of a family of Mn⁴⁺-activated alkaline hexafluoride salts.     

Submillimeterwave spectrum of CH2PH and equilibrium structures of CH2PH and CH2NH

The rotational spectrum of phosphaethene (CH₂PH) was reinvestigated. One hundred and nineteen new lines were measured in the submillimeter range from 500 to 650 GHz. The determination of the centrifugal distortion constants is significantly improved. As the molecule is close to symmetric prolate top, both reduction A and S were compared. The equilibrium structure has been derived from experimental ground state rotational constants and ab initio rovibrational interaction parameters. This semi-experimental structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quintuple-zeta quality and a core correlation correction. The structure of CH₂PH was compared to that of CH₂NH which was also determined for this goal. It is found that the semi-experimental structure of CH₂NH is less accurate than the ab initio structure. It is also found that the methylene group is much more asymmetric in CH₂NH than in CH₂PH.     

New high-resolution analysis of the {ν1 + ν3} band of the NO2 isotopomer of nitrogen dioxide: Line positions and intensities

The high-resolution Fourier transform absorption spectrum of an isotopic sample of nitrogen dioxide, ¹⁵N¹⁶O₂, was recorded in the 3.4 μm region. Starting from the results of a previous study [Y. Hamada, J. Mol. Struct. 242 (1991) 367-377] a new analysis of the ν₁ + ν₃ band located at 2858.7077 cm⁻¹ has been performed. This new assignment concerns (1 0 1) energy levels involving rotational quantum numbers up to K_a = 10 and N = 54. Using a theoretical model which accounts for both the electron spin-rotation resonances within each vibrational state and the Coriolis interactions between the (1 2 0) and (1 0 1) vibrational states, the spin-rotation energy levels of the (1 0 1) vibrational state could be reproduced within their experimental uncertainty. In this way, the precise vibrational energy, rotational, spin-rotation, and coupling constants were achieved for the {(1 2 0), (1 0 1)} interacting states of ¹⁵N¹⁶O₂. Using these parameters and the transition moment operator which was obtained for the main isotopic species, ¹⁴N¹⁶O₂, a comprehensive list of the line positions and intensities was generated for the ν₁ + ν₃ band of ¹⁵N¹⁶O₂.     

Theoretical investigation of ESR spectra and local structure for VO in Ba2Zn(HCOO)6(H2O)

The electron spin resonance spectra (characterized by g factors g_, g_⊥ and hyperfine structure constants A_ and A_⊥) of Ba₂Zn(HCOO)₆(H₂O) (BZFA): VO²⁺ crystal are calculated from high order perturbation formulas. The calculated results are in good agreement with the observed values. The local structure parameters of [VO(H₂O)₅]²⁺ clusters are also obtained from the calculation. The magnitudes of the metal-ligand distances parallel and perpendicular to the C₄-axis are, respectively, R_≈0.163 nm and R_⊥≈0.210 nm. It is shown that the local structure around the V⁴⁺ ion possesses a compressed tetragonal distortion along C₄-axis.     

The ν1 + 3ν2 + 3ν3 and 4ν1 + ν2 + ν3 bands of ozone by CW-cavity ring down spectroscopy between 5900 and 5960 cm

The absorption spectrum of ozone, ¹⁶O₃, has been recorded in the 5903-5960 cm⁻¹ region by high sensitivity CW-cavity ring down spectroscopy (α_min ∼ 5 × 10⁻¹⁰ cm⁻¹). The ν₁ + 3ν₂ + 3ν₃ and 4ν₁ + ν₂ + ν₃ A-type bands centred at 5919.15 and 5947.07 cm⁻¹ were newly observed. A set of 173 and 168 energy levels could be experimentally determined for the (1 3 3) and (4 1 1) states, respectively. Except for a few K_a = 5 levels of the (4 1 1) state, the rotational structure of the two states was found mostly unperturbed. The spectroscopic parameters were determined from a fit of the corresponding line positions by considering the (1 3 3) and (4 1 1) states as isolated. The determined effective Hamiltonian and transition moment operators were used to generate a list of 785 transitions given as Supplementary Material.