Ba原子6s6p1P1←6s6s1S0跃迁的光腔衰荡光谱

建立了一套光腔衰荡原子束吸收光谱测量装置,并对Ba原子的6s6p¹P₁←6s6s¹S₀吸收谱线用光腔衰荡光谱方法进行了测量,得到了Ba原子在553.548nm不同温度下的吸收谱线线型.实验结果表明,该装置测量吸收灵敏度达到6×10^-7. 关键词： 光腔衰荡 吸收光谱 Ba原子     

Electronic energy transfer from Cd(53P1 to Popop vapor

Quenching of Cd(5³P₁) by POPOP and sensitization of POPOP by Cd(5³P₁) have been investigated in the vapor phase at total pressures of 10^-1 to 10^-2 torr. Quenching of Cd is observed to occur at a rate of 5.9 X 10^-10 cm³/sec and sensitization of POPOP at a rate of 4.2 X 10^-11 cm³/sec. The sensitized fluorescence rate has been found to be consistent with Forsters long-range dipole-dipole mechanism. Selection of a donor for a possible energy transfer, vapor phase, dye laser is discussed.     

Ion-electron coincidence study of the thermal He(23S) + H2 Penning reaction

A new Penning-electron-Penning-ion coincidence method is described. It is applied to the study of the thermal reaction of He(2³S) with H₂. The main results reported are separate electron energy spectra that are coincident with the three different ions formed: HeH₂⁺, HeH⁺ and H₂⁺. Based on these results it is shown that the Penning reaction of the He(2³S)/H ₂ system proceeds in two well-separated steps: (i) ionization at distances R (HeH₂) ? 6a₀ in which H₂⁺ (v) is formed in different vibrational states; and (ii) reactive collision of H₂⁺ (v) with He. For the second step the variation of the branching ratios with vibrational quantum numbers v = 0 to v = 10 is derived, and it is shown that these branching ratios may be regarded as relative vibrational-energy-dependent cross-sections for the collision of H₂⁺ (v) with He at an average relative kinetic energy of ～20 meV.     

Acetylene spectra with a tunable diode laser: (ν4 + ν5)0+−ν41fQ branches of 12C2H2 and 12C13CH2

The rotational structure of the Q branches of the (ν₄ + ν₅)⁰⁺?ν₄^1f bands of ¹²C₂H₂ and ¹²C¹³CH₂ at 13.7 μm has been observed in a natural sample of acetylene by using a tunable diode laser as a source in a high-resolution infrared grating spectrometer equipped with a precision grating drive. Altogether 23 lines from J = 6 to 28 for ¹²C₂H₂ and 15 lines from J = 6 to 20 for ¹²C¹³CH₂ have been identified. The observed full width at half maximum of the resolved lines of these Q branches is very close to the calculated Doppler width. Molecular constants ν₀ + B″, B′ ? B″ ? 2D″, D′ ? D″, and H′ ? H″ have been derived from the measured line positions of the rotational structure.     

Analytical potential energy function for the electronic states 2^∏1/2 and 2^∏3/2 of O^x2 （x=＋1, -1）

The splitting of potential energy levels for ground state X^2∏g of O^x2 （x = ＋1,-1） under spin-orbit coupling （SOC） has been calculated by using the spin-orbit （SO） multi-configuration quasi-degenerate perturbation theory （SO-MCQDPT）. Their Murrell-Sorbie （M S） potential functions are gained, and then the spectroscopic constants for electronic states 2^∏1/2 and 2^∏3/2 are derived from the M S function. The vertical excitation energies for O^x2 （x = ＋1,-1） are v[O2＋1^（2∏3/2→X^2∏1/2）] =195.652cm^-1, and v[O2^-1（2^∏1/2 →X^2∏3/2）] =182.568cm^-1, respectively. All the spectroscopic data for electronic states 2^∏1/2 and 2^∏3/2 are given for the first time.     

BeH,H2和BeH2的分子结构和势能函数

用二次组态相关(QCISD)和密度泛函(B3LYP)方法, 选用6-311++g(d,p), 6-311++g(3df,3pd)和D95(3df,3pd)基组对H₂, BeH和BeH₂分子的结构进行优化. 得到它们的基态电子态分别为H₂(¹Σ_g), BeH(²Σ)和BeH₂(¹Σ_{g 关键词： BeH 2}')" href="#">BeH₂ 2')" href="#">H₂ 二次组态相关(QCISD) 势能函数     

Velocity dependence of the chemi-ionization of H2O and D2O on impact of 21S and 23S helium atoms

The velocity dependence for the ionization of H₂O and D₂O to form H₂O⁺ and D₂O⁺ in collisions with both 2³S and 2¹S metastable helium atoms has been measured in a crossed molecular beam apparatus using a mechanical velocity-selector on the metastable beam. The cross-sections are found to be proportional to the —n power of the relative collision energy, with n ? 0.4 for both metastable atoms in both gases. The branching ratios H₂O⁺/OH⁺ and D₂O⁺/OD⁺ were both found to be 4.3 for both metastable helium atoms, and to be independent of the relative collision energy.     

High-Resolution Stimulated Raman Spectroscopy of Cl2, Cl2, and ClCl

A high-resolution rovibrational Raman spectrum of a sample of Cl₂ has been recorded at room temperature using a quasi-cw stimulated Raman technique. Three Q-branch structures belonging to the fundamental vibrations of the three chlorine isotopomers present in the sample in natural abundances and two weaker Q branches belonging to the first hot bands of the two more abundant isotopomers, ³⁵Cl₂ and ³⁵Cl³⁷Cl, have been observed. Lines with values of J up to 60 for the fundamentals and 50 for the hot bands have been measured in these fully resolved structures. Some additional lines belonging to O and S branches of the fundamentals and hot bands have also been recorded. The analysis of these data has rendered a new and more precise set of rotational molecular constants and band origins for the first three vibrational states of the chlorine isotopomers.     

Charmonium-the 1P1 state

Based on a model which gives agreement with the observed hyperfine and fine splitting of the charmonium states, we predict the mass of ¹p₁ to be 3372 MeV, substantially lower than any previous predicted values. We have also estimated branching ratios and decay rates for the production of this state via channels which become accessible because of its low mass.     

Analysis of the nuclear quadrupole interaction of Disulfur Dichloride, S2Cl2

Pure rotational spectra of S₂³⁵Cl₂ and S₂³⁵Cl³⁷Cl have been observed using a Fourier-transform microwave spectrometer. An analysis of the hyperfine structure made by considering the nuclear spin statistics showed that S₂Cl₂ has C₂symmetry, where the hyperfine splittings due to the two Cl nuclei were analyzed precisely. The nuclear quadrupole coupling constants including the off-diagonal (χ_ab, χ_ac, χ_bc) components and the nuclear spin–rotation interaction constants associated with the two Cl nuclei have been determined for the first time. We have shown that the nuclear quadrupole interaction plays an important role in the ortho–para mixing.     

Spectroscopically determined potential energy surfaces of the H2O, H2O, and H2O isotopologues of water

Adiabatic potential energy surfaces (PESs) for three major isotopologues of water, H₂¹⁶O, H₂¹⁷O, and H₂¹⁸O, are constructed by fitting to observed vibration-rotation energy levels of the system using the nuclear motion program DVR3D employing an exact kinetic energy operator. Extensive tests show that the mass-dependent ab initio surfaces due to Polyansky et al. [O.L. Polyansky, A.G. Császár, S.V. Shirin, N.F. Zobov, P. Barletta, J. Tennyson, D.W. Schwenke, P.J. Knowles, Science 299 (2003) 539-542.] provide an excellent starting point for the fits. The refinements are performed using a mass-independent morphing function, which smoothly distorts the original adiabatic ab initio PESs. The best overall fit is based on 1788 experimental energy levels with the rotational quantum number J = 0, 2, and 5. It reproduces these levels with a standard deviation of 0.079 cm⁻¹ and gives, when explicit allowance is made for nonadiabatic rotational effects, excellent predictions for levels up to J = 40. Theoretical linelists for all three isotopologues of water involved in the PES construction were calculated up to 26 000 cm⁻¹ with energy levels up to J = 10. These linelists should make an excellent starting point for spectroscopic modelling and analysis.     

The rotational a-type sepctra of 15N-labeled diazirine,H2CN2

The rotational a-type spectra of isotopically enriched diazirine isotopomers, H₂¹²C¹⁴N¹⁵N and H₂¹²C¹⁵N₂, have been recorded in the region between 8 and 300 GHZ; the latter isotopomer has been observed for the first time. Using Watson's A-reduced Hamiltonian, the rotational constants and the quartic and some sextic centrifugal distortion constants have been determined for the ground vibrational states.     

Spin--orbit ab initio curves of 80Se2+ ion and theassignment of photoelectron spectra of 80Se2 molecule

This paper carries out ab initio calculations to study the ^80Se2（X^3Σg^-） state and ^80Se2^＋（X^2Πg）, ^80Se2^＋（a^4Πg） states by using completed active space self-consistent field and multi-reference second order perturbation theory. The electronic curves of these states including spin-orbit coupling are calculated, and then the spectroscopic parameters are obtained. The photoelectron spectra of ^80Se2 molecule in gas phase are assigned according to Franck-Condon analysis based on calculated potential energy curves. The ionization energies of ^80Se2 molecule are determined by the present calculation.     

Determination of the coupling constants 3Hdn, 3Hπ and 3He3Heπ from data on the differential cross sections OF n3H and n3He elastic scattering

A determination of the coupling constants ³Hdn, ³H³H_π and ³He³He_π from existing differential cross section data for n³H and n³He elastic scattering has been carried out. The method is based on the extrapolation of dσ/dΩ to the deuteron and pion poles, exploiting conformal mapping techniques. Calculations result in a value of the ³Hdn coupling constant which is ≈ 20% smaller than dispersion relation predictions. A comparison of the value obtained with predictions based on nuclear models allows one to discriminate between different potentials. The residue at the pion pole turns out to be too weak and the conclusion is drawn that it is impossible to determine the coupling constants ³H³H_π and ³He³Heπ on the basis of existing data.     

Higher overtones of the bending vibrations of the ground states of 12CS2 and 13CS2

Large numbers of ‘hot’ bands in the first electronic absorption systems of ¹²CS₂ and ¹³CS₂ have been analyzed from plates taken at high dispersion, and accurate rotational constants have been obtained for the overtones of the ground state bending vibration up to v₂ = 6 and l = 3 for ¹²CS₂ and v₂ = 4, l = 2 for ¹³CS₂. The energy differences between the various levels with the same l value have been determined to an accuracy of about ±0.006 cm^?1, but (because of the parallel polarization of the electronic transition) the absolute energies of levels with l > 0 cannot be obtained.     

Pure rotational spectra of 32SF535Cl, 32SF537Cl,and 34SF535Cl up to 300 GHz

Pure rotational spectra of the three molecules ³²SF₅³⁵Cl, ³²SF₅³⁷Cl, and ³⁴SF₅³⁵Cl in their ground vibrational states have been observed up to 300 GHz (8 < J < 80). Molecular parameters have been computed with good accuracy for the three isotopic species. The “K-type” splitting characteristic of molecules belonging to the C_4v symmetry group has been clearly seen and measured.     

EPR studies of Gd3+-doped Ce2(SO4)3.8H2O and La2(SO4)3.9H2O single crystals

EPR spectra of Gd³⁺-doped Ce₂(SO₄)₃.8H₂O and La₂(SO₄)₃.9H₂O single crystals have been measured with an X-band spectrometer at room and low temperatures. The absolute signs of spin Hamiltonian parameters have been determined for the La₂(SO₄)₃.9H₂O host from intensities of lines at liquid helium temperature; for the Ce₂(SO₄).8H₂O host the lines broaden considerably below 60 K, not permitting the determination of absolute signs of spin Hamiltonian parameters. The data are analysed using a rigourous least-squares procedure, fitting simultaneously all lines obtained for several orientations of the external magnetic field. The zero-field splittings have been computed for both the hosts. The characteristics of EPR spectra of Gd³⁺ in these hosts are compared with those obtained in other rare-earth trisulphate octahydrate hosts.     

7Li2分子23Πu激发态的解析势能函数、振动能级及其转动惯量

使用Gaussian 03程序包中的“对称性匹配簇-组态相互作用”方法、在0.13—2.0nm的核间距范围内利用6-311+〖KG-*3〗+G(d,p)基组对⁷Li₂(2³Π_u)分子的势能曲线进行了计算, 同时使用最小二乘法将计算结果拟合成了解析势能函数. 利用拟合出的解析势能函数并结合Rydberg-Klein-Rees方法, 计算了该态的谐振频率, 进而计算了该态的其他光谱常数, 分别为T关键词： 解析势能函数 谐振频率 振动能级 转动惯量     

Crystal field parameters and energy level structure of the MnO4 tetroxo anion in Li3PO4, Ca2PO4Cl and Sr5(PO4)3Cl crystals

A comparative study concerning the electronic structure of the Mn⁵⁺ ion in the Li₃PO₄, Ca₂PO₄Cl, Sr₅(PO₄)₃Cl host lattices has been carried out in the framework of the exchange charge model. The crystal field parameters have been evaluated using the structural data as the only input information. The 10 K absorption spectra of the investigated compounds have been measured in order to verify the correspondence between experimental and calculated energy levels. A systematic trend of the crystal field splitting of the most intense transitions has been evidenced and discussed by considering the symmetry properties of the coordination polyhedra around Mn⁵⁺.     

Theoretical study of stereodynamics for the reaction O(3P) +D2 (v=0, j=0) to OD+D and isotope effect

Quasi-classical trajectory (QCT) calculations have been performed to study the product polarization behaviours in the reaction O(³P) + D₂ (v= 0, j= 0)→OD + D. By running trajectories on the ³A′ and ³A″ potential energy surfaces (PESs), vector correlations such as the distributions of the polarization-dependent differential cross sections (PDDCSs), the angular distributions of P(θ_r) and P(ø_r) are presented. Isotope effect is discussed in this work by a comprehensive comparison with the reaction O(³P) + H₂ (v= 0, j= 0) → H + H. Common characteristics as well as differences are discussed in product alignment and orientation for the two reactions. The isotope mass effect differs on the two potential energy surfaces: the isotope mass effect has stronger influence on P(θ_r) and PDDCSs of the ³A′ PES while the opposite on P(ø_r) of the ³A″ potential energy surface.