Accurate theoretical spectroscopic investigations of the 20 Λ-S and 58 Ω states of O2+ cation including the spin–orbit coupling effect

The potential energy curves (PECs) are calculated for the 20 Λ-S states (X²Π_g, A²Π_u, B²Σ^?_g, a⁴Π_u, b⁴Σ^?_g, b′⁴Π_g, c⁴Σ^?_u, 1²Σ⁺_g, 1²Σ⁺_u, 1²Σ^?_u, 1⁴Σ⁺_g, 1⁴Σ⁺_u, 1⁴Δ_g, 1⁴Δ_u, 1⁶Σ⁺_g, 1⁶Σ⁺_u, 1⁶Π_g, 1⁶Π_u, 2⁴Π_g and 2⁴Π_u) of O₂⁺ cation and their corresponding 58 Ω states. Of these 20 Λ-S states, the 1⁶Π_u state is found to be repulsive. The 1²Σ⁺_g, 1⁴Σ⁺_u, c⁴Σ^?_u and 1⁴Δ_u states are found to possess the double well. The b⁴Σ^?_g, 1⁶Σ⁺_g, 1⁴Σ⁺_u, a⁴Π_u, A²Π_u, 1⁶Π_g and 2⁴Π_g states are found to be inverted with the spin–orbit coupling effect included. The b′⁴Π_g, 1⁶Π_g, 1⁶Σ⁺_g, 1⁴Σ⁺_u and 1⁴Δ_u states, and the second well of the 1²Σ⁺_g state are found to be the weakly bound states. The b′⁴Π_g state is found to possess one well with one barrier. The PECs are calculated by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson correction in combination with the aug-cc-pV6Z basis set. The core–valence correlation and scalar relativistic corrections are included. The convergent behaviour of present calculations is discussed with respect to the basis set and theoretical level. The spin–orbit coupling effect is accounted for. The PECs are extrapolated to the complete basis set limit. The spectroscopic parameters are evaluated, and compared with available measurements. It demonstrates that the spectroscopic parameters reported here can be expected to be reliably predicted ones.     

Rydberg states of carbon dioxide and carbon disulfide

The electronic absorption spectra of carbon dioxide and carbon disulfide have been reexamined. Model potential calculations have been used to calculate the energies of excited states in Rydberg approximation, and (npσ) and (npπ) Rydberg series have been assigned. For both molecules, the lowest excited ¹Π_g and ¹Π_u states are identified as Rydberg states. The lowest ${}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state is mainly Rydberg for CO₂, but contains some valence character for CS₂, There is no evidence for transitions to additional valence states of these symmetries.It is shown that $\text{LCAO}\text{MO}$ predictions about excited states can be misleading because of near-linear dependencies which arise in multicenter expansions. A consideration of the united atom orbitals for CO₂ and CS₂ predicts that there should be only the number of low-energy excited states which are found from the spectral analysis.     

Li2分子自旋一致激发态a3Σ+u和b3Πu的分析势能函数的从头算

使用对称性匹配簇-组态相互作用方法首次计算了Li₂分子自旋一致激发态a³Σ⁺_u和b³Π_u的离解能、平衡几何及其谐振频率。使用最小二乘法、利用Murrell-Sorbie函数形式拟合出了Li₂分子三重态的第一激发态a³Σ⁺_u 和第二激发态b³Π_u的完整势能函数，并计算了这两个态的光谱常数 (B_e, α_e, ω_e 和 ω_eχ_e) 和力常数 (f₂, f₃和f₄)。得到了Murrell-Sorbie函数形式既适用于基态、又适用于激发态的结论。将计算得到的激发态（a³Σ⁺_u和b³Π_u）的离解能、平衡几何及其谐振频率与实验结果及其它理论计算结果进行了比较。从比较的结果中可以清楚地看出，本文的计算结果在计算精度方面有很大的改进。     

The origin of K2, Rb2 and Cs2 triplet 13Πg−X3Σ+u bands in discharge

The absorption and emission spectra of potassium, rubidium and caesium low-pressure discharges have been studied at the far blue wings of resonance D2-lines. The observed diffuse bands were attributed to the 1³Π_g?X³Σ⁺_u transition. Experiments revealed the recombination ²P + ²S nature of these bands, and the corresponding rate coefficients were obtained. Energies of the higher excited states as well as the X³Σ⁺_u -state well depths for K₂, Rb₂ and Cs₂ molecules were estimated.     

Ab initio calculation of transition dipole moments for transitions between valence states in oxygen molecules

Results of ab initio calculations of potential-energy curves for 20 singlet and 20 triplet valence states of oxygen with configuration interaction taken into account in the 6-31G basis are presented. Transition dipole moments of triplet-triplet (1³Π_g ← B ³Σ _u ^? , 1³Π_g ← A ³Σ _u ⁺ , 1³Π_g ← A′ ³Δ_u, B ³Σ _u ^? ← X ³Σ _g ^? , 2³Π_u ← 1³Π _g, 2³Σ _g ^? ← B ³Σ _u ^? , 1³Π_u ← X ³Σ _g ^? , 2³Π_u ← X ³Σ _g ^? , 2³Π _g ← A′³Δ_u, 3³Π_g ← A′ ³Δ _u, 2³Δ_u ← 2³Π_g, 3³Π_g ← B ³Σ _u ^? , and 2³Π_g ← A ³Σ _u ⁺ ) and singlet-singlet (2¹Σ _g ⁺ ← 2¹Π_u, 2¹Π_u ← 1¹Π ^g, ¹Π_u ← 2¹Δ_g, 1¹Π_g ← c ¹Σ _u ^? , ¹Π_u ← b ¹Σ _g ⁺ , 1¹Δ _u ← a ¹Δ_g, 2¹Π_u ← a ¹Δ_g, 2¹Δ_g ← 1¹Δ_u, ¹Π _u ← a ¹Δ _g, 1¹Π_u ← b ¹Σ _g ⁺ , 2¹Π_g ← 1¹Π_u, 2¹Π _g ← c ¹Σ _u ^? , 1¹Δ _u ← 1¹Π _g, f′Σ _u ⁺ ← b ¹Σ _g ⁺ , 2¹Σ _g ⁺ ← f ′¹Σ _u ⁺ , 3¹Π_g ← 1¹Δ_u) radiative transitions are calculated as functions of internuclear separation. The possibility of observing these transitions under experimental conditions is discussed.     

用能量自洽法研究碱金属双原子分子的势能曲线

用能量自洽法(ECM)研究了碱金属双原子分子一些电子激发态的势能曲线：Na₂ 分子的2¹Π_g,4³Π_g和b³Π< sub>u电子激发态,K₂分子的a³Σ^＋_{u,2¹Πg,B¹Πu和A^{关键词： 能量自洽 双原子分子 势能 碱金属}}     

The formation of excited CO2+ ions by vacuum ultraviolet radiation

Excited CO₂⁺ ions are formed by irradiating CO₂ molecules with the synchrotron radiation. The excitation function of CO₂⁺ (B?²Σ_u⁺) shows a pronounced structure which can be explained by an interaction of the Rydberg states npπ_u converging to C²Σ_g⁺ with the continuum of B?²Σ_u⁺.     

On the photoelectron spectrum of CS2

High-resolution photoelectron spectra of CS₂ have been obtained by photoionization with the He(I) (58.4 nm), Ne(I) (73.58–74.37 nm) and Ar(I) (104.8–106.7 nm) resonance lines. The resolution of about 17 meV was further improved by deconvolution of the experimental data. The formation of the X?²Π_g and B?²Σ_u⁺ states is accompanied by a weak ν₂ excitation. The spin—orbit splitting of the òΠ_u state is completely resolved, and a value of 186 cm^?1 is reported. We confirm the value of 12.689 eV for the ionization threshold of the Ã²Π ^u3/2 state, and show that the small peak observed at lower energy is due to a hot band.     

Analytical potential energy functions for the ground and some excited states of N2

The analytical potential energy functions have been calculated for the ground state X¹Σ⁺_g and four excited electronic states a¹Π_g, A³Σ⁺_u, B′³Σ^?_u and B³Π_g of N₂ molecule using the algebraic and energy-consistent methods (AM-ECM). Based on our previously published full AM vibrational energies and spectroscopic constants, the low-lying force constants f_n, the expansion coefficients a_n and the variational parameters λ in the AM–ECM potentials are determined for these states. The computed AM–ECM potential energy curve of each state is in excellent agreement with the experimental data and better than other analytical potentials.     

Laser transitions among the C1Πu, 31Σg+, A1Σu+, and X1Σg+ states of Na2

Intense infrared stimulated lines at wavelengths around 2.5 μm have been observed upon excitation of Na₂ by uv radiation from a frequency-doubled narrow-band dye laser. Frequencies of these IR lines have been measured when the pump laser was tuned to C¹Π_u ← X¹Σ_g⁺ assigned transitions in the wavelength range 331–334 nm. High-resolution spectroscopy measurements of the involved rovibrational levels of both C¹Π_u and 3¹Σ_g⁺ electronic states allow the unambiguous assignment of these IR laser lines to C¹Π_u → 3¹Σ_g⁺ transitions.     

Spectroscopic and molecular properties of 14 selected electronic states of Si2 molecule

The potential energy curves (PECs) of the X³Σ_g⁻, D³Π_u, a¹Δ_g, b¹Π_u, H′³Σ_u⁻, K³Σ_u⁻, 1³Σ_u⁺, 1³Π_g, 2³Σ_u⁺, 2³Π_g, 3³Π_g, 3³Σ_u⁺, 2³Π_u and 2³Σ_g⁻ electronic states of the Si₂ molecule are investigated using the complete active space self-consistent field (CASSCF) method followed by the valence internally contracted multireference configuration interaction (MRCI) approach with the correlation-consistent basis sets of Dunning and co-workers. The effects on the PECs by the core-valence correlation and relativistic corrections are included. The way to consider the relativistic correction is to use the third-order Douglas-Kroll Hamiltonian approximation. The core-valence correlation correction is made with the aug-cc-pCV5Z basis set. And the relativistic correction is performed at the level of cc-pV5Z basis set. To obtain more reliable results, the PECs determined by the MRCI calculations are also corrected for size-extensivity errors by means of the Davidson modification (MRCI+Q). The PECs of all these electronic states are extrapolated to the complete basis set limit by the total-energy extrapolation scheme. Using the PECs, the spectroscopic parameters are determined and compared with those reported in the literature. With these PECs determined by the MRCI+Q/CV+DK+56 calculations, the vibrational levels and inertial rotation constants of the first 20 vibrational states are evaluated and compared with the RKR data for these electronic states when the rotational quantum number J equals zero. On the whole, as expected, the most accurate spectroscopic parameters and molecular constants of the Si₂ molecule are determined by the MRCI+Q/CV+DK+56 calculations. And the spectroscopic parameters of the 1³Σ_u⁺, 1³Π_g, 2³Σ_u⁺, 2³Π_g, 3³Π_g, 3³Σ_u⁺, 2³Π_u and 2³Σ_g⁻ electronic states obtained by the MRCI+Q/CV+DK+56 calculations should be good prediction for future laboratory experiment.     

Observation of the c3Πu-X1Σg+ intersystem transition in the absorption spectrum of P2

The observation of the c³Π_u-X¹Σ_g⁺ intersystem transition of P₂ is reported. The 6-0 band of the system was identified on high resolution absorption plates teken on the NRC 10-m vacuum spectrograph at Ottawa. A rotational analysis of the band is given together with that of the adjacent 5-0 band of the C¹Σ_u⁺-X¹Σ_g⁺ system, the upper level of which is involved in a mutual perturbation with the c³Π_u, v = 6 level. The interaction parameters for the perturbation are derived. It is proposed that the appearance of the 6-0 band of the c³Π_u-X¹Σ_g⁺ transition is due to intensity borrowing from the strong, allowed C¹Σ_u⁺-X¹Σ_g⁺ system. Accurate values for the energies of the c³Π_u, b³Π_g, and a³Σ_u⁺ states relative to the ground state are given. The analysis of two other bands, 2-0 and 7-0, of the C¹Σ_u⁺-X¹Σ_g⁺ system whose upper levels likewise interact strongly with the c³Π_u state are also given.     

Study of the covalent and triplet ionic-pairing states of the fluorine molecule with the MRDCI method

The results of nonempirical calculations of the electronic structure, spectroscopic constants, and potential-energy curves for the covalent and triplet ionic-pairing states of the F₂ molecule are presented. It is shown that the covalent 1³Π_u state is weakly bound, with the depth of the potential well of this state being of about 0.05–0.2 eV. The effect of the spin-orbital interaction on the ionic-pairing states, which can result in the perturbation of the Ω=0⁺ and Ω=1 components of the ³Σ _u ^? and ³Π_u states, is analyzed. It is demonstrated that the lasing observed at λ ≈ 157 nm is caused by the transitions between the ionic-pairing state 2³Π_g and the weakly bound covalent state 1³Π_u.     

S2分子B″3Πu态的势能函数和光谱常数的理论研究

推导了S₂分子B″³Π_u态的合理离解极限.用Gaussian 94 QCISD(T)方法和6-311++G^**基组计算了S₂分子B″³Π_u以及X³Σ^-_g态的势能曲线.给出了S₂分子B″³Π_u态的Murrell-Sorbie势能函数和光谱常数.B″³Π_u与B³Σ^-_u态在排斥支重叠范围大；同时，B″³Π_u与X³Σ^-_g态有相同离解极限，因而，在吸引支有重叠.讨论了B″³Π_u与B³Σ^-_u和X³Σ^-_g态相互作用的特征. 关键词：     

Fluorescence of Na2 and K2 excited by a gold vapor laser

The gold vapor laser has been used to irradiate the alkali dimers Li₂, Na₂, K₂, and Rb₂. Significant fluorescence was found only from Na₂ and K₂. Six fluorescent series in the A¹Σ_u⁺-X¹Σ_g⁺ system of Na₂ and three in the B¹Π_u-X¹Σ_g⁺ system of K₂ were assigned, respectively. New spectroscopic constants for the X¹Σ_g⁺ state of ³⁹K₂ are derived, and new RKR potential energy curves for the X¹Σ_g⁺ and B¹Π_u states of ³⁹K₂ are given.     

Inelastic scattering and satellite fine structure in the high-resolution uv photoelectron spectrum of CS2

The outer valence region in CS₂ has been studied by high-resolution UV photpelectron Spectroscopy. The spectra reveal detailed vibrational structure in the X$\text{\$}\text{?}$²Π_g, A$\text{\$}\text{?}$²Π_u, B$\text{\$}\text{?}$²Σ⁺_u and C$\text{\$}\text{?}$²Σ⁺_g bands. Some of the fine-structure peaks in the X$\text{,}\text{?}$B$\text{\$}\text{?}$and C$\text{\$}\text{?}$bands are shown to be pressure-dependent. The reason for the pressure dependence is assumed to be inelastic scattering of electrons emitted in the adiabatic transitions. It is established that the two CI satellite bands present in the He(I)-excited spectrum contain vibrational structure.     

分子部分电子态的高阶振动能级和离解能的精确研究

鉴于K₂分子电子态的振动能谱和分子离解能D_e在实际研究和应用中的重要性,应用Sun,Ren等人提出的基于微扰理论的代数方法(AM)和基于AM的代数能量方法(AEM)研究了K₂分子的X¹Σ⁺_g,a³Σ⁺_u,0^-_g,B¹Π_{u< 关键词： 2}分子')" href="#">K₂分子 代数方法 高阶振动能级 离解能     

Photoionization of molecular oxygen in the X3Σg− and a1Δg states

Calculations are carried out, at similar levels of approximation, of the photoionization cross-sections for the ground X³Σ_g^? and metastable a¹Δ_g states of O₂ leading to the X²Π_g state of O₂⁺. Estimates, based upon measurements for the X³Σ_g^? state, are made of the photoionization cross-section of the a¹Δ_g state for transitions populating excited states of O₂⁺.     

Electronic transition dipole moment functions and difference potentials for transitions among low-lying states of Li2 and Na2

Electronic transition dipole moment functions based on ab initio multiconfiguration self-consistent field wavefunctions are computed for the transitions ¹Σ_u⁺-¹Σ_g⁺, ³Σ_g⁺-³Σ_u⁺, ¹Π_u-¹Σ_g⁺, ³Π_g-³Σ_u⁺, ¹Σ_u⁺-¹Π_g, ³Σ_g⁺-³Π_u, ¹Π_u-¹Π_g, and ³Π_g-³Π_u in Li₂ and Na₂. (In each case the states are the lowest lying of their symmetry.) We also calculate the matrix element 〈³Σ_u⁺|i(L_x - iL_y)|³Π_u〉 for the predissociation of the ³Π_u state by the ³Σ_u⁺ state. Several unobserved spectral features are predicted.     

Spectroscopic study of an rf discharge in nitrogen

The absolute populations of the vibrational levels of the B³Πg and C³Π_u states in an rf nitrogen discharge are calculated from the quantum yields of the 1⁺ and 2⁺ systems in the discharge, and the “excitation temperature” of these states is measured. Emission spectroscopic methods are used to determine the vibrational and rotational temperatures of the C³Π_u state, as well as the vibrational temperature of the B³Π_g state. These data are used to estimate the vibrational temperature of the X′∑ _g ⁺ state and the stored energy in the activated nitrogen, and to examine the mechanism by which translational-vibrational degrees of freedom are excited in nitrogen molecules in the discharge.