Calculation of adiabatic potentials of Li<Subscript>2</Subscript><Superscript>+</Superscript>

We report adiabatic potential energy curves of the Li₂ ⁺ molecule. Our curves are tabulated according to internuclear distance from 2 a₀ to 100 a₀. We compare our theoretical results with the ones calculated by other authors and potential energy curves derived from experiments. For the ground state and 17 excited states we calculate spectroscopic parameters and compare them with parameters obtained by other authors. For the first time we present three new minima for 3²Σ_u ⁺, 4²Σ_u ⁺ and 2²Π_g excited states. In our approach we use the configuration interaction method where only the valence electrons of Li atoms are treated explicitly. The core electrons are represented by pseudopotential. All calculations are performed by means of MOLPRO program package.     

Perturbations in the rotational structure of the 4<Emphasis Type="Italic">p</Emphasis> complex of H<Subscript>2</Subscript> molecule terms

A statistical analysis of all the available data on the wave numbers of spectral lines related to triplet-triplet electronic-vibrational-rotational (rovibronic) radiation transitions into the H₂ molecule (1sσ2sσ) a ³Σ _g ⁺ electronic state was performed for the first time. This allowed us to check and refine the controversial identification of several spectral lines. Optimum rovibronic term values were found for 15 electronic states, including the (4pσ)f ³Σ _u ⁺, (4pπ)k ³Π _u ⁺, and (4pπ)k ³Π _u ⁻ states studied in this work. The ratios between the oscillator strengths of R- and P-branch lines with common upper levels (branching coefficients) for the f ³Σ _u ⁺ → a ³Σ _g ⁺ and k ³Π _u ⁺ → a ³Σ _g ⁺ systems of H₂ molecule bands were measured for the first time. Substantial deviations of the measured branching coefficients from the corresponding ratios between the Henl-London factors were observed. The deviations monotonically increased as the rotational quantum number N grew, which, in combination with substantial Λ-doubling in the k ³Π _u state, was evidence of an important role played by electronicrotational interaction in the 4pσ³Σ _u ⁺ and 4pπ³Π _u ⁺ adiabatic electronic states. A strong correlation was observed between the N dependences of branching coefficients for transitions from the mutually perturbed f ³Σ _u ⁺ and k ³Π _u ⁺ electronic states. The results of this work show that the measured branching coefficients are a much more sensitive and capacious channel of information about perturbation effects than rovibronic term values.     

The E(4) Πu state in K2 and its perturbations

The E(4) ¹Π_u←X ¹Σ⁺_g band system of the K₂ molecule is investigated by the technique of Doppler-free optical–optical double resonance polarization spectroscopy. The observed vibrational levels v=0 to 9 of the E state are subject to numerous rotational perturbations by the neighboring 4 ³Π_u, 4 ¹Σ⁺_u, and 5 ³Σ⁺_u electronic states. By using deperturbation methods, the potential curves of the 4 ¹Π_u and 4 ³Π_u states are determined as well as some properties of the 4 ¹Σ⁺_u and 5 ³Σ⁺_u state potentials. The results are compared with predictions of ab initio calculations.     

Experimental determination of the potential energy curves of the I(3/2u) and I(3/2g) states of Kr+ 2

The I(3/2u) and I(3/2g) states of Kr⁺ ₂ have been investigated by pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy following (2 + 1′) resonance-enhanced multiphoton excitation via the 0⁺ _g Rydberg state located below the Kr?([4p]⁵5p[1/2]₀) + Kr(¹S₀) dissociation limit of Kr₂. From the positions of a large number of vibrational bands in the spectra of the ⁸⁴Kr₂ and ⁸⁴Kr-⁸⁶Kr isotopomers, the adiabatic ionization potentials (IP(I(3/2u)) = 112672.4 ± 0.8cm^?1, IP(I(3/2g)) = 111 395.0 ± 1.4cm^?1), the dissociation energies (D ⁺ ₀(I(3/2u)) = 368.8 ± 2.0cm^?1, D ⁺ ₀(I(3/2g)) = 1646.2 ± 2.3cm^?1) and vibrational constants for both ionic states have been determined. Potential energy curves have been extracted which perfectly reproduce all experimental observations and are accurate over a wide range of energies and internuclear distances. The equilibrium internuclear distances (R ⁺ _e(I(3/2u)) = 4.11 ± 0.04 Å, R ⁺ _e(I(3/2g)) = 3.35 ± 0.10 Å) have been derived by comparing the intensity distribution in the PFI-ZEKE photoelectron spectra to calculated Franck-Condon factors. The dissociation energy of the I(3/2g) state and the equilibrium internuclear distance of the I(3/2u) state differ markedly from previously reported values.     

Momentum transfer dependence behaviors of ionization and dissociation of oxygen

The decay pathways of the structured ionization region of oxygen at different momentum transfers,i.e.,0,0.23 a.u.(atomic unit),and 0.91 a.u.,are studied by measuring the ion and the scattered electron coincidently.It is found that the dipole-forbidden superexcited states of(2σu)-1(c4Σu-)npσu 3Σg-← X3Σg-decay into different channels according to the principal quantum number n.The broad ridge above 35 eV,which may be due to inner-valence excited states of(2σg)-1nλ or multiply excited states,is observed both at small and large momentum transfers,and its decay channel of O++ O is dominant.     

Frequency measurements in the b <Superscript>3</Superscript>Π(0<Subscript>u</Subscript><Superscript>+</Superscript>) - X <Superscript>1</Superscript>Σ<Subscript>g</Subscript><Superscript>+</Superscript> system of K<Subscript>2</Subscript>

Absolute transition frequencies of the b ³Π(0_u ⁺) - X ¹Σ_g ⁺ system of K₂ were measured in a molecular beam with Lamb dip absorption spectroscopy applying a frequency comb from a femtosecond pulsed laser. Both, K atoms and K₂ molecules are present in the beam and are expected to interact by collisions. The atoms can be deflected optically out of the beam, and thus the collision rate between K atoms and K₂ molecules is changed by about an order of magnitude. The molecular transition frequencies for low collisional rate are compared with those for high one. Limits for the collisional frequency shift within the beam are determined.     

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.     

Dipole moment functions for electronic transitions from ion-pair states of the second tier of molecular iodine

The emission spectra caused by the transitions from the ion-pair states and f0 _g ⁺ and G1_g of the I₂ molecule are obtained by excitation of individual rovibronic levels of the molecule by the method of optical-optical double resonance. The emission spectra from the state F0 _u ⁺ populated due to collisions I₂(f) + I₂(X) are also measured. By modeling the experimental emission spectra, the dipole moment functions for the electronic transitions f _g ⁺ -B0 _u ⁺ , A0 _u ⁺ , and B″0 _u ⁺ ; G1_g-A0 _u ⁺ and B″0 _u ⁺ ; and F0 _u ⁺ -X0 _g ⁺ and a′0 _g ⁺ of the iodine molecule are reconstructed.     

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     

High sensitive photoassociation spectroscopy based on modulated ultra-cold Cs atoms

In this paper, a high sensitive photoassociation spectroscopy based on modulated ultra-cold cesium atoms is reported. The cold cesium gas in the magneto-optical trap is illuminated by a photoassociation laser with red detuning 40 cm^-1 below the 6S _1/2+6P _3/2 dissociation limit and photoassociation to the excited state ultra-cold molecules is observed. The rotationally bound levels of 0_g ^- state are well resolved using the lock-in detection. The 0_g ^-, 1_g and 0_u ⁺ long range states which connect to this dissociation limit are measured. The long-range dipole–dipole interaction constants are determined through a fit of the experimental energy levels. PACS 33.15.Mt; 33.20.Vq; 32.80.Pj     

Variational calculations on the hydrogen molecular ion

We present high-precision non-relativistic variational calculations of bound vibrational—rotational state energies for the H⁺ ₂ and D⁺ ₂ molecular ions in each of the lowest electronic states of Σ _g , Σ _u , and Π _u symmetry. The calculations are carried out including coupling between Σ and Π states but without using the Born—Oppenheimer or any adiabatic approximation. Convergence studies are presented which indicate that the resulting energies for low-lying levels are accurate to about 10^?13. Our procedure accounts naturally for the lambda-doubling of the Π _u state.     

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.     

Photostimulated electron transfer and its action on paramagnetism of Sp<Subscript>3</Subscript>Cr(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript> single crystals

The effect of irradiation by ultraviolet light on the effective magnetic moment of a paramagnetic single crystal based on photochrome spiropyran (Sp) and chromium oxalates Sp₃Cr(C₂O₄)₃ molecules is detected. It is shown that the deviation of the temperature dependence of the magnetic moment from the Curie law is caused not by the exchange interaction, but by electron redistribution between Cr³⁺ and Cr⁴⁺ ions and spiropyran molecules Sp⁰ and Sp⁺. Analysis of the angular dependence of EPR spectra makes it possible to determine the contribution of Cr³⁺ ions to the magnetic properties of the crystals and to determine the crystal field parameters D = 0.619 cm⁻¹ and E = 0.024 cm⁻¹. Irradiation of hydrated samples by ultraviolet light leads to intensity redistribution of EPR lines attributed to Cr³⁺ and Sp⁰. Thermally stimulated paramagnetism of triplet states of spiropyran ions Sp⁺ and the SpI salt is observed.     

Calculation of spectroscopic constants and radiative parameters for A1Σ u+ -X1Σ g+ and B1Πu-X1Σ g+ electronic transitions of sodium dimer

Vibrational, rotational, and centrifugal spectroscopic constants and radiative parameters, i.e., the Einstein coefficients, oscillator strengths, and wave numbers for vibrational transitions in electronic systems of bands A ¹Σ _u ⁺-X ¹Σ _g ⁺ (0 ≤ v′ ≤ 25; 0 ≤ v″ ≤ 44), B ¹Π _u -X ¹Σ _g ⁺ (0 ≤ v′ ≤ 29; 0 ≤ v″ ≤ 47), and the radiative lifetimes for the vibrational levels of excited states of the sodium dimer, are calculated. The calculations are carried out based on semiempirical potential curves constructed in this study. The calculated spectroscopic constants and radiative lifetimes are compared to the experimental values.     

Laser-induced breakdown spectra of Zn2 molecule in the violet region

Laser-induced breakdown spectrum has been recorded in the region of 380–455 nm using second harmonics of Nd:YAG laser, computer-controlled TRIAX 320 M monochromator with a reciprocal linear dispersion 2.64 nm/mm fitted with ICCD detector. The spectrum consists of 108 bands, which are classified into four new subsystems E0 _u ⁺ (¹Σ _u ⁺ ) → A1_g(³Π_g), J0 _g ^± \1_g(³Σ _g ⁺ ) → D1_u(¹Π_u), F1_u → A0 _g ^± (³Π_g) and F1_u → A2_g(³Π_g) along with additional bands of the known system E0 _u ⁺ (¹Σ _u ⁺ ) → A0 _g ^± (³Π_g). The molecular constants for these systems have also been determined.     

The analysis of nitrogen rotational and vibrational bands in a helium microhollow gas discharge

Emission spectroscopy is applied to measure the gas temperature T _g and the vibrational distribution of N₂ (C ³Π_u) and N₂ ⁺(B ²Σ_u ⁺) excited states from a helium microhollow gas discharge (MHGD) at atmospheric pressure. The rotational temperature T _rot of N₂ ⁺ is determined from relative intensity of the R‐branch lines of the N₂ ⁺(B ²Σ_u ⁺–X ²Σ_g ⁺) bands at 427.81 and 419.91 nm and the well‐known Boltzmann plot (BP). Using the same diagnostic technique, the rotationally resolved N₂(C ³Π_u–B ³Π_g) band at 380.49 nm is used to measure T _rot. Under our experimental conditions, T _g is equal to T _rot = 550–650 K for nitrogen molecules and shows a slight increase with the discharge current in the current range 3–10 mA. From the intensity ratio of two consecutive vibrational bands of the same sequence, the N₂(C ³Π_u) and N₂ ⁺(B ²Σ_u ⁺) vibrational temperature T _vib = 3,700–4,000 K is determined. It has been found that N₂ ⁺(B ²Σ_u ⁺) ions have non‐Boltzmann distribution in the helium MHGD, while N₂(C ³Π_u) molecules are populated according to the Boltzmann distribution. Following the Franck–Condon principle, the vibrational distribution of the ground state of N₂(X ¹Σ_g ⁺) molecules has been determined from the N₂(C ³Π_u) distribution using the inversion matrix of elements q _XC(ν ,ν ′).     

Kinetic ion-acoustic solitary waves in collisional plasmas

In this study, a bipolar high-voltage pulse with 20 ns rising time is employed to generate diffuse dielectric barrier discharge plasma using wire-plate electrode configuration in nitrogen at atmospheric pressure. The gas temperature of the plasma is determined by comparing the experimental and the best fitted optical emission spectra of the second positive bands of N₂(C³Π_u → B³ Π_g, 0-2) and the first negative bands of N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0). The effects of the concentration of argon and oxygen on the emission intensities of N₂ (C³Π_u → B³Π_g, 0-0, 337.1 nm), OH?(A ²Σ → X²Π, 0-0) and N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm) are investigated. It is shown that the plasma gas temperature keeps almost constant with the pulse repetition rate and pulse peak voltage increasing. The emission intensities of N₂ (C³Π_u → B³Π_g, 0-0, 337.1 nm), OH(A²Σ → X²Π, 0-0) and N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm) rise with increasing the concentration of argon, but decrease with increasing the concentration of oxygen, and the influences of oxygen concentration on the emission intensities of N₂(C³Π_u → B³Π_g, 0-0, 337.1 nm) and OH (A²Σ → X²Π, 0-0) are more greater than that on the emission intensity of N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm).     

Optical characteristics of radiation from N<Stack><Subscript>2</Subscript><Superscript>*</Superscript></Stack> dimers in a barrier discharge

The spectral and power characteristics of radiation of the second positive system of nitrogen (C ³Π _u → B ³Π _g ) in Ar-N₂ and Ar-N₂-Cl₂ mixtures excited by barrier discharge have been studied experimentally. Addition of argon to N₂ increased the radiation power by sixfold. In the triple mixture Ar-N₂-Cl₂ = 210/0.5/0.005, minor chlorine additions increased the intensity of the C ³Π _u → _B ³Π _g transition by 26% compared to Ar-N₂ mixtures. Radiation power density of 2.7 mW/cm² has been achieved. In both binary and triple mixtures, the second positive system of nitrogen was the major contributor to radiation, while the contributions of the fourth positive system of N ₂ ^* (D ³Σ _u ⁺ → B ³Π _g ), the Vegard-Kaplan transition of N ₂ ^* (A ³Σ _u ⁺ → X ¹Σ _g ⁺ ), and the D′ → A′ band of Cl ₂ ^* were negligibly small.