Rotational Analysis of the 1–4 Band of the B 2Σ+–X 2Σ+ System of 14C16O+

ABSTRACT

High-resolution emission spectrum of the 1–4 band of the B ²Σ⁺–X ²Σ⁺ transition of ¹⁴C¹⁶O⁺ was observed for the first time by conventional emission spectroscopy. The band spectrum was excited in a water-cooled Geissler lamp filled with commercial gaseous carbon monoxide enriched in about 80% of the radiocarbon ¹⁴C. A rotational analysis has been carried out and obtained molecular constants have been merged with previously published data for the B ²Σ⁺–A ²Π_i and A ²Π_i–X ²Σ⁺ transitions. The principal equilibrium constants for the ground X ²Σ⁺ state obtained from this work are ω_e = 2121.7726(98), ω_e x _e = 13.9055(27), B _e = 1.815290(30), α_e = 1.6594(33) × 10^?2, and γ_e = ? 0.377(73) × 10^?4 cm^?1. Also, presently known experimental equilibrium molecular constants of the X ²Σ⁺ states of the CO⁺ isotopic molecules are summarized and isotopic dependence of the B _e and ω _e constants is discussed.     

The X2Π and A2Σ+ states of FH+, ClH+ and BrH+: theoretical study of their g -factors and fine/hyperfine structures

Theoretical calculations on the fine, hyperfine and Zeeman (g-factor) parameters are reported for the X²Π and A²Σ⁺ states of FH⁺, ClH⁺ and BrH⁺. The fine-structure constants [spin–orbit (A), Λ-doubling (p, q) and spin–rotation constants (γ _Π, γ _Σ)] are evaluated up to second order (via SO/L couplings with several excited states) using a multireference configuration interaction (MRCI) method, a Breit–Pauli Hamiltonian and 6-311++(2d,2pd) basis sets. Hyperfine constants of magnetic and electric type [Frosch–Foley (a, b, c, d) and nuclear quadrupole (eQq ₀, eQq ₂)] are studied with density functional methods and various basis sets. Magnetic dipole moments (parameterized via g-factors) are calculated in second order like the fine structure constants. The situation is somewhat complex for X²Π since no less than five different g’s have to be evaluated in second order. In general, our results are in good agreement with those reported in the literature, mostly limited to the ground state. Our calculations confirm that, at equilibrium, all second-order properties are dominated by the couplings between the electronic states X and A.     

Low energyK + scattering onN =Z nuclei

The data for the total cross-section ofK ⁺ scattering on various nuclei have been analysed in the Glauber multiple scattering theory. Energy-dependentK ⁺ -nucleus optical potential is generated using the forwardK ⁺ -nucleon scattering amplitude and the nuclear density distribution. Along with this, the calculated totalK ⁺ -nucleus cross-sections using the effectiveK ⁺ -nucleon crosssection inside the nucleus are also presented.     

The B 2Σ+–X 2Σ+ Transition of 12C17O+: The 2‐υ″ Progression

Abstract

Three new bands of the B ²Σ⁺–X ²Σ⁺ system of ¹²C¹⁷O⁺ have been investigated using conventional spectroscopic techniques. The spectra were observed in a graphite hollow‐cathode lamp by discharging molecular oxygen (enriched in about 45% of the ¹⁷O₂ isotope) under 1.0 Torr pressure. The rotational analysis of the 2–4, 2–5, and 2–6 bands was performed with the effective Hamiltonian of Brown (Brown et al., J. Mol. Spectrosc. 1979; 74: 294–318). Molecular constants were derived from a merge calculation, including both the current wavenumbers and the spectroscopic data published by the authors previously. The principal equilibrium constants for the ground state of ¹²C¹⁷O⁺ are ω_e=2185.9658(84), ω_e x _e = 14.7674(11), B _e=1.927001(38), α_e=1.8236(22)×10^?2, γ_e=?0.331(28)×10^?4, D _e=6.041(12)×10^?6, β_e=0.100(31)×10^?7 cm^?1, and the equilibrium constants for the excited state are σ_e=45876.499(15), ω_e=1712.201(12), ω_e x _e=27.3528(39), B _e=1.754109(35), α_e=2.8706(57)×10^?2, γ_e = ?1.15(19)×10^?4, D _e=7.491(20)×10^?6, β_e=2.13(12)×10^?7, γ_e = 2.0953(97)×10^?2, and α_γe=?9.46(59)×10^?4 cm^?1, respectively. Rydberg–Klein–Rees potential energy curves were constructed for the B ²Σ⁺ and X ²Σ⁺ states of this molecule, and Franck–Condon factors were calculated for the vibrational bands of the B–X system.     

Evolution of chirality from γ soft Ru to triaxial Ru

Rotational bands in ^108,110,112Ru have been investigated by means of γ–γ–γ and γ–γ(θ) coincidences of prompt γ rays emitted in the spontaneous fission of ²⁵²Cf. The positive parity bands are described by different versions of IBA, where ¹⁰⁸Ru is best described as a γ-soft nucleus whereas ^110,112Ru are more like rigid triaxial rotors. New ΔI=1 negative parity doublet bands are found. In case of ^110,112Ru, these are interpreted as soft chiral vibrations. Many of the experimental findings can be explained by microscopic calculations that combine the TAC mean-field with random phase approximation but a simple geometrical explanation is not apparent.     

Theoretical calculation of of B-like ions： photoionization cross sections N^2＋, O^3＋ and F^4＋

There can be found some notable discrepancies with regard to the resonance structures when R-matrix calculations from the Opacity Project and other sources are compared with recent absolute experimental measurements of Bizau et al [Astron.Astrophts.439 387(2005)] for B-like ions N2+,O3+ and F4+.We performed close-coupling calculations based on the R-matrix formalism for the photoionizations of ions mentioned above both for the ground states and first excited states in the near threshold regions.The present results are compared with experimental ones given by Bizau et al and earlier theoretical ones.Excellent agreement is obtained between our theoretical results and the experimental photoionization cross sections.The present calculations show a significant improvement over the previous theoretical results.     

Enhancement of upconversion luminescence in Tm/Er/Yb-codoped glass ceramic containing LiYF4 nanocrystals

A transparent Er³⁺–Tm³⁺–Yb³⁺ tri-doped oxyfluoride glass ceramics containing LiYF₄ nanocrystals were prepared. Under 980 nm laser diode (LD) pumping, intensive red, green and blue upconversion (UC) was obtained. The blue, green, and red UC radiations correspond to the transitions ¹G₄→³H₆ of Tm³⁺, ²H_11/2/⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2 of Er³⁺ ions, respectively. This is similar to that in Tm³⁺–Yb³⁺ and/or Er³⁺–Yb³⁺ co-doped glass ceramics. However, the blue UC radiations of the Er³⁺–Yb³⁺ co-doped glass ceramics is two-photon process due to cooperative energy transfer. The UC mechanisms were proposed based on spectral, kinetic, and pump power dependence analyses.     

Einstein<Emphasis Type="Italic">A</Emphasis>-coefficients for rotational transitions in the ring-chain isomer of C<Subscript>5</Subscript>H<Subscript>2</Subscript>

Laboratory formation of four isomers of C⁵H² molecule is reported and detection of the ring-chain isomer (isomer 1) of C₅H₂ in cosmic objects has been suggested. For identification of a molecule in cosmic objects, one of the required input data is EinsteinA-coefficients (radiative transition probabilities) for the molecule. Here, we report EinsteinA-coefficients for electric dipole transitions in the ring-chain isomer of C₅H₂ among the rotational levels of the ground electronic and ground vibrational states up to 21 cm⁻¹.     

Rotational analysis of the 0–9, 0–10 and 0–11 bands of theA 2II u -X 2II g band system of (16O18O)+

High-resolution spectra of the 0–9, 0–10 and 0–11 bands of theA ²II _u —X ²II _g system of (¹⁶O¹⁸O)⁺ ion have been studied for their rotational structure. This study enables a direct determination of the Λ-doubling parameters of theA ²II _u andX ²II _g states. The model of ‘pure precession’ explains, though not entirely, the Λ-doubling of theX ²II _a state as arising out of its interaction with theB ² Σ _g ⁻ state. The Λ-doubling in theA ²II _u state was found insignificant.     

Optical parameters of Nd3＋：Er3＋：yb3＋ co-doped borosilicate glasses and their energy transfers at high temperature

This paper reports that a series of Nd³⁺:Er³⁺:Yb³⁺ co-doped borosilicate glasses have been prepared and their absorption spectra measured. The J--O intensity parameters Ω_k (k=2, 4, 6), spontaneous radiative lifetime τ_rad, spontaneous transition probability A, fluorescence branching ratio β and oscillator strength f_ed of the Nd³⁺ ions at room temperature are calculated based on Judd--Ofelt (J--O) theory. The temperature dependence of the up-conversion photoluminescence characteristics in a Nd³⁺:Er³⁺:Yb³⁺ co-doped sample is studied under a 978 nm semiconductor laser excitation, and the energy transfer mechanisms among Yb³⁺, Er³⁺ and Nd³⁺ ions are analysed. The results show that the J--O intensity parameters Ω₂ increase when the Nd³⁺ concentration of the Nd³⁺:Er³⁺:Yb³⁺ co-doped borosilicate glasses increases. The possibility of spontaneous transition is small and lifetimes are long at levels of ⁴F_5/2 and ⁴F_3/2. The intensity of Nd³⁺ emissions at 595, 691, 753, 813 and 887 nm are markedly enhanced when the sample temperature exceeds 400 K. The reasons being the cooperation of the secondary sensitization from Er³⁺ to Nd³⁺ and the contribution of a multi-phonon.     

Atom in a femtosecond bichromatic laser field

The ionization of real hydrogen atom is studied under the action of a two-color pulsed laser field of duration 2.12 fs consisting of a fundamental frequencyω and one of its harmonics. We study the effect of phase difference (φ betweenω and its harmonic on the ionization probability. It is found that ionization can be switched on and off by varying the relative phaseφ betweenω and its harmonic.     

Quantitative Evaluation of the Lactate Signal Loss and Its Spatial Dependence in PRESS Localized H NMR Spectroscopy

Localized ¹H NMR spectroscopy using the 90°−t₁−180°−t₁+t₂−180°−t₂−Acq. PRESS sequence can lead to a signal loss for the lactate doublet compared with signals from uncoupled nuclei which is dependent on the choice of t₁ and t₂. The most striking signal loss of up to 78% of the total signal occurs with the symmetrical PRESS sequence (t₁=t₂) at an echo time of 2/J (290 ms). Calculations have shown that this signal loss is related to the pulse angle distributions produced by the two refocusing pulses which leads to the creation of single quantum polarization transfer (PT) as well as to not directly observable states (NDOS) of the lactate AX₃ spin system: zero- and multiple-quantum coherences, and longitudinal spin orders. In addition, the chemical shift dependent voxel displacement (VOD) leads to further signal loss. By calculating the density operator for various of the echo times TE=n/J, n=1, 2, 3, …, we calculated quantitatively the contributions of these effects to the signal loss as well as their spatial distribution. A maximum signal loss of 75% can be expected from theory for the symmetrical PRESS sequence and TE=2/J for Hamming filtered sinc pulses, whereby 47% are due to the creation of NDOS and up to 28% arise from PT. Taking also the VOD effect into account (2 mT/m slice selection gradients, 20-mm slices) leads to 54% signal loss from NDOS and up to 24% from PT, leading to a maximum signal loss of 78%. Using RE-BURP pulses with their more rectangular pulse angle distributions reduces the maximum signal loss to 44%. Experiments at 1.5 T using a lactate solution demonstrated a maximum lactate signal loss for sinc pulses of 82% (52% NDOS, 30% PT) at TE=290 ms using the symmetrical PRESS sequence. The great signal loss and its spatial distribution is of importance for investigations using a symmetrical PRESS sequence at TE=2/J.     

High-resolution emission spectroscopy of the AΠ–XΣ system of AlH

The emission spectrum of the A²Π–X²Σ⁺ system of the AlH⁺ ion was investigated in the range of 27 000–29 000 cm⁻¹ by using a conventional spectroscopic technique. The AlH⁺ molecules were formed and excited in an aluminium hollow-cathode lamp with two anodes, filled with a mixture of Ne carried gas and a trace of NH₃. The emission from the discharge was observed with a plane grating spectrograph and recorded by a photomultiplier tube. The full rotational structure of the 0-0 and 1-1 bands has been observed for the first time (12 branches up to J″ = 36.5) and many new constants of the X²Σ⁺ state have been derived from the analysis. For the A²Π, v = 0 and 1 state a considerable irregularities of the Λ-doubling have been observed. The most reasonable explanation for this anomaly is an interaction with unstableness rotational levels of X²Σ⁺ state and perturbing of the A²Π state by the nearly lyingB²Σ⁺ state.     

Deuterium-deuterium fusion by an activated precursor

Summary A general scheme is proposed for the interpretation of the phenomena involving low-energy hydrogen-isotope fusion. This scheme is especially developed for the interpretation of the fusion rate observed after the impact of heavy-water clusters (D₂O) _n , 25≲n≲1350, onto targets of titanium deuteride TiD. It is shown that 1) the impinging energy of large clusters or molecules is equiparted among a lot of target atoms which are brought in collective motion; 2) data can conveniently be represented in an Arrhenius plot; 3) this plot suggests that fusion is a thermally activated process from a metastable precursor; 4) the activation energy for the precursor formation isE ^*≃2E ₀ (E ₀ being the electron binding energy in the hydrogen atom), and 5) the activated precursor can reasonably be identified with the metastable binuclear heliumlike (D⁺D⁺)2e⁻ atom.     

Pr3+/Ho3+共掺Ge-Ga-Se玻璃的2.9 μm荧光特性的研究

采用熔融冷却法制备了系列Ho³⁺/Pr³⁺共掺的Ge₂₅Ga₁₀Se₆₅玻璃样品,测试了样品的吸收光谱以及908 nm激光抽运下的中红外荧光光谱和Ho³⁺离子⁵I₇能级寿命.计算了Ho³⁺:⁵I₇→⁵I₈发射截面和Pr³⁺:³H₄→³F₂吸收截面,讨论了Ho³⁺,Pr³⁺离子之间的能量转移效率及Pr³⁺离子浓度的影响.通过拟合Ho³⁺离子2.0 μm荧光衰减曲线判断能量转移机理.结果表明,Ho³⁺掺杂Ge₂₅Ga₁₀Se₆₅玻璃中引入Pr³⁺离子可以有效提高Ho³⁺离子的2.9 μm荧光强度. 关键词： 中红外发光 硫系玻璃 3+/Pr³⁺共掺')" href="#">Ho³⁺/Pr³⁺共掺     

Improved techniques for the calculation of ab initio ion-neutral interaction potentials: application to coinage metal ions interacting with rare gas atoms

Ab initio values for the potential energy functions for ion–neutral interactions can be tested by comparison with gaseous ion transport coefficients, but only if special care is taken to compute the interaction potentials accurately over wide ranges of internuclear separation. This is illustrated here by a reanalysis of the ab initio values for the coinage metal ions interacting with rare gas atoms, precise calculations of the transport cross sections over extremely wide ranges of energy, and similarly precise calculations of the zero-field ion mobilities as functions of gas temperature and the field-dependent ion mobilities at various fixed temperatures. The calculations indicate that the mobilities for Ag⁺(¹S) moving in Ne or Ar can distinguish between the existing, very similar ab initio potentials. They also show that substantial differences exist among the mobilities of the coinage metal anions and the ground and excited states of the cations. The techniques implemented are recommended for future ab initio calculations.     

One- and two-dimensional C–H/N–H dipolar correlation experiments under fast magic-angle spinning for determining the peptide dihedral angle φ

A recently proposed ¹³C–¹H recoupling sequence operative under fast magic-angle spinning (MAS) [K. Takegoshi, T. Terao, Solid State Nucl. Magn. Reson. 13 (1999) 203–212.] is applied to observe ¹³C–¹H and ¹⁵N–¹H dipolar powder patterns in the ¹H–¹⁵N–¹³C–¹H system of a peptide bond. Both patterns are correlated by ¹⁵N-to-¹³C cross polarization to observe one- or two-dimensional (1D or 2D) correlation spectra, which can be simulated by using a simple analytical expression to determine the H–N–C–H dihedral angle. The 1D and 2D experiments were applied to N-acetyl[1,2-¹³C,¹⁵N] -valine, and the peptide φ angle was determined with high precision by the 2D experiment to be ±155.0°±1.2°. The positive one is in good agreement with the X-ray value of 154°±5°. The 1D experiment provided the value of φ=±156.0°±0.8°.     

Microwave assisted IMDAF# reaction: Microwave irradiation applied with success to cycloaddition reaction of N-propargyl-N-p-tolyl-N-2-furfurylamines

The new tertiary furfurylamine with triple bond as a dienophylic part i. e. N-(5-methyl-2-furfuryl)-N-prop-2-ynyl-p-toluidine (1) was prepared and the intramolecular Diels-Alder reaction of the amine (1) was performed under microwave irradiation conditions and by heating a benzene solution of the amine under nitrogen. Comparing the results of the usual thermal and the MAOS reaction, we confirmed our expectations that MAOS could promote the outcome of IMDA reaction of the suitably N-substituted tertiary 2-furfuryl-amines. In the present example, N-p-tolyl-5-methyl-5,7a-dihydro-5,7a-epoxyisoindoline was obtained in much better yield and of higher purity.The acronym for: Intramolecular Diels-Alder Reaction of Furan.The acronym for: Microwave-Assisted Organic Synthesis.     

Algebraic method of determining bond length of perovskite compounds doped with Mn

An algebraic method is proposed for calculating the exponent n and constant K in the power law 10Dq=KR⁻ⁿ. By using this method, the values of n and K for the cubic perovskites KMnF₃ and RbMnF₃ are derived and then used to determine the true Mn²⁺–F⁻ bond length R in crystals of KMgF₃, KZnF₃, RbCdF₃, and CsCaF₃ doped with Mn²⁺ from the reported optical spectra. The results obtained are in good agreement with those derived from the electron paramagnetic resonance data and the extended X-ray absorption fine structure techniques. Thus, as a new theoretical method, it is valuable and convenient for the determination of the bond lengths.     

共沉淀法制备Y2SiO5∶Er3+ ,Yb3+ ,Tm3+及其上转换发光性能研究

采用化学共沉淀法制备了系列Y_1.98-2xYb_2x Er_0.02SiO₅(0.00≤x≤0.15)以及Y_1.736Yb_0.24Er_0.02Tm_0.004SiO₅上转换发光材料,比较了室温下Y_1.98-2xYb_2x Er_0.02 SiO₅ (x=0.00,0.08)样品在400—1600 nm范围内的吸收光谱,测量了所有样品在976 nm OPO激光器激发下的上转换发射光谱,以及Er³⁺离子⁴S_3/2(⁴F_9/2)→⁴I_15/2,Tm³⁺离子¹G₄→³H₆荧光衰减曲线和不同激发功率下的上转换蓝光发射强度,从而分析讨论了Er³⁺,Tm³⁺在Y₂SiO₅中的上转换发光机理.研究结果表明:在1250 ℃相对较低的温度下合成了X2型单斜晶系Y₂SiO₅ ∶Ln³⁺(Ln³⁺=Er³⁺,Yb³⁺,Tm³⁺),Yb³⁺的敏化显著增强了样品在976 nm附近的吸收能力,并大幅度加宽了该处的吸收带.分析上转换发射光谱发现:上转换绿光和红光强度都随着Yb³⁺浓度的增加先增强后减弱,但红光的猝灭浓度较高,归因于Er³⁺→Yb³⁺反向能量传递ETU4和Yb³⁺→Er³⁺正向能量传递ETU3过程的发生;上转换蓝光发射是三光子吸收过程,是通过Yb³⁺,Tm³⁺之间三次声子辅助的能量转移方式实现的. 关键词： 上转换 共沉淀 2SiO₅∶Er³⁺')" href="#">Y₂SiO₅∶Er³⁺ 3+')" href="#">Yb³⁺ 3+')" href="#">Tm³⁺