Molecule opacities of X~2Σ~+, A~2Π, and B~2Σ~+ states of CS~+

Carbon sulfide cation(CS~+) plays a dominant role in some astrophysical atmosphere environments. In this work, the rovibrational transition lines are computed for the lowest three electronic states, in which the internally contracted multireference configuration interaction approach(MRCI) with Davison size-extensivity correction(+Q) is employed to calculate the potential curves and dipole moments, and then the vibrational energies and spectroscopic constants are extracted. The Frank–Condon factors are calculated for the bands of X~2~+Σ~+–A~2Π and X~2Σ~+–B~2Σ~+systems, and the band of X~2Σ~+–A~2Π is in good agreement with the available experimental results. Transition dipole moments and the radiative lifetimes of the low-lying three states are evaluated. The opacities of the CS~+ molecule are computed at different temperatures under the pressure of 100 atms. It is found that as temperature increases, the band systems associated with different transitions for the three states become dim because of the increased population on the vibrational states and excited electronic states at high temperature.     

Accurate potential energy function and spectroscopic study of the X~2Σ~+,A~2Ⅱ and B~2Σ~+ states of the CP radical

This paper calculates the equilibrium internuclear separations,the harmonic frequencies and the potential energy curves of the X 2 Σ +,A 2Ⅱ and B 2 Σ + states of the CP radical by the highly accurate valence internally contracted multireference configuration interaction method with correlation-consistent basis sets(aug-cc-pV6Z for C atom and aug-cc-pVQZ for P atom).The potential energy curves are all fitted with the analytic potential energy function by the least-square fitting.Employing the analytic potential energy function,we determine the spectroscopic constants(B e,α e and ω e χ e) of these states.For the X 2 Σ + state,the obtained values of D e,B e,α e,ω e χ e,R e and ω e are 5.4831 eV,0.792119 cm 1,0.005521 cm 1,6.89653 cm 1,0.15683 nm,12535.11 cm 1,respectively.For the A 2Ⅱ state,the present values of D e,B e,α e,ω e χ e,R e and ω e are 4.586 eV,0.703333 cm 1,0.005458 cm 1,6.03398 cm 1,0.16613 nm,1057.89 cm 1,respectively.For the B 2 Σ + state,the present values of D e,B e,α e,ω e χ e,R e and ω e are 3.506 eV,0.677561 cm 1,0.00603298 cm 1,5.68809 cm 1,0.1696 nm,822.554 cm 1,respectively.For these states,the vibrational states with the rotational quantum number J equals zero(J = 0) are studied by solving the radial nuclear Schro¨dinger equation using the Numerov method.For each vibrational state,the vibrational level,the classical turning points,the rotational inertial and the centrifugal distortion constants are calculated.Comparison is made with recent theoretical and experimental results.     

Perturbation Facilitated Optical-Optical Double Resonance spectroscopy of the 6Li233Σg+, 23Πg, 13Δg,b3Πu,and a3Σu+ states

The technique, Perturbation Facilitated Optical-Optical Double Resonance, has provided spectroscopic access to and molecular constants for the 3³Σ_g⁺ (v = 1–9), 2³Π_g (v = 0–24), 1³Δ_g (v = 3–14), b³Π_u (v = 0–17), and a³Σ_u⁺ (v = 0–6) states of the ⁶Li₂ molecule. Perturbation Facilitated Optical-Optical Double Resonance takes advantage of two weak spin-orbit perturbations, A¹Σ_u⁺ (v = 2, J = 33) ∼ b³Π_u (v = 9, F₁, N = 32) and A¹Σ_u⁺ (v = 9, J = 20) ∼ b³Π_u (v = 15, F₁, N = 19), to excite from X¹Σ_g⁺ (v = 0 or 1) into single rotation-vibration levels of ³Λ_u (F₁ fine structure component only) via the spin-mixed intermediate levels. The ³Λ_u (F₁ only) states are sampled in resolved fluorescence spectra from Perturbation Facilitated Optical-Optical Double Resonance-populated ³Λ_g levels.     

icMRCI+Q理论研究Cl_2~+离子 X~2Π_g和A~2Π_u态的光谱性质

利用考虑Davidson修正的内收缩多参考组态相互作用(icMRCI+Q)方法结合相关一致基组aug-cc-pV6Z计算了Cl_2~+离子X~2Π_g和A~2Π_u态及其它们所产生的4个Ω态的势能曲线.为了提高势能曲线的可靠性和精确性,计算中考虑了旋轨耦合效应、核价相关和标量相对论修正.基于得到的势能曲线,获得了X~2Π_g、A~2Π_u态和4个Ω态的光谱常数和振动能级,与已有的实验结果非常符合.分析表明首次报道的A~2Π_(u,1/2)态的光谱常数以及X~2Π_g, A~2Π_u, A~2Π_(u,3/2)和A~2Π_(u,1/2)态的振动能级也应是可靠的.     

CW Optical-Optical Double Resonance studies of the 23Πg, 33Πg, 43Πg+, and 13Δg Rydberg states of Na2

The 2³Π_g, 3³Π_g, 4³Σ_g⁺, and 1³Δ_g states of the Na₂ molecule are observed by sub-Doppler Perturbation Facilitated Optical-Optical Double Resonance (PFOODR) spectroscopy. Absolute vibrational assignments and molecular constants are obtained for two of these states (3³Π_g, v = 0–25 observed, and 4³Σ_g⁺, v = 3–5, 13, 14 observed). Tentative vibrational assignments and provisional molecular constants are obtained for the 2³Π_g (v = 43–89 observed) and 1³Δ_g (v = 31–35, 40, 46–51 observed) states. Spin-orbit, spin-spin, and hyperfine splittings are observed. The direct ³Λ_g⁺ → a³Σ_u, 2³Π_g ∼ 3³Π_g perturbation-induced, and collision-induced contributions of these four ³Λ_g states to the ubiquitous Na-vapor violet and ultraviolet emission bands are discussed.     

Rotational analysis of the c3Πu–b3Πg system of P2

The rotationally resolved spectra of the c³Π_u–b³Π_g system of P₂ in the 16620–17860 cm^?1 region is reanalyzed here to obtain more assignments of the rotational lines and more accurate molecular constants. Approximately 500 spectral lines were assigned to six subbands: the Ω=0, 1 and 2 components of the (2, 3) band, the Ω=0 and 2 components of the (1, 3) band and the Ω=2 component of the (1, 2) band. Because of perturbations in the c³Π_u (υ=2) state, the Λ-doubling in the ³Π₂–³Π₂ subband of the (2, 3) band was resolved. By the weighted nonlinear least-squares fitting using two types of effective Hamiltonians, more accurate molecular constants for the υ′=1 and 2 levels in the c³Π_u state and for the υ″=2 and 3 levels in the b³Π_g state of P₂ were derived.     

Calculation of molecular constants for the X 1Σ g + , A 1Σ u + , B 1Πu, and a 3Σ u + electronic states of 39K2

The molecular constants are calculated for the X ¹Σ _g ⁺ , A ¹Σ _u ⁺ , B ¹Π_u, and a ³Σ _u ⁺ and electronic states of a potassium dimer. The wave functions and vibrational energies necessary for calculating the molecular constants are determined by solving the radial wave equation with the use of potential energy curves constructed by the semiempirical method. The vibrational terms, the rotational constants, and the centrifugal distortion constants calculated from the potential curves are compared with those determined from the experimental data.     

High resolution Fourier spectroscopy of P2 infrared emission spectrum: Analysis of two new systems b3Πg → w3Δu and A1Πg → W1Δu

The investigation of the emission infrared spectrum of P₂ was performed with a high resolution Fourier spectrometer. Two new electronic systems were attributed to b³Π_g → w³Δ_u and A¹Π_g → W¹Δ_u transitions. The molecular parameters are obtained by a complete fitting procedure. The main equilibrium constants of the new states are (in cm^?1):

$\text{ω}{}^3\text{Δ}{}_{\mathrm{u}}\text{T}{}_{\mathrm{e}}\text{= 243228.07 ω}{}_{\mathrm{e}}\text{= 591.3 ω}{}_{\mathrm{e}}\text{X}{}_{\mathrm{e}}\text{= 2.5}$

$\text{B}{}_{\mathrm{e}}\text{= 0.256040 δ}{}_{\mathrm{e}}\text{= 0.001409 D}{}_{\mathrm{e}}\text{= 19.0 X 10}{}^{\mathrm{?8}}$

$\text{W}{}^1\text{Δ}{}_{\mathrm{u}}\text{T}{}_{\mathrm{e}}\text{= 31096.64 W}{}_{\mathrm{e}}\text{= 627.206 W}{}_{\mathrm{e}}\text{X}{}_{\mathrm{e}}\text{= 2.331}$

$\text{B}{}_{\mathrm{e}}\text{= 0.2628 δ}{}_{\mathrm{e}}\text{= 0.0014 D}{}_{\mathrm{e}}\text{= 23 X 10}{}^{\mathrm{?8}}$

     

Formation of N2 C3Πu and B3Πg by dissociative recombination of Ar 2 + in Ar+N2 early afterglow

The hf pulse excited Ar + N₂ mixtures and early afterglow are investigated at total pressures from 266 to 1995 Pa using nitrogen of 0·05–0·5% concentration. The time-resolved intensity of Ar I atomic lines and N₂ (2nd pos., 1st pos. and 1st neg.) band systems exhibit an intense early afterglow (0·3 ms). Both the decay of electron densityn _e and that of molecular Ar ₂ ⁺ ions and enhancement of coefficient of dissociative recombination due to electron temperature decrease after the pulse lead to the formation of characteristic secondary maximum of Ar I spectral line and N₂ molecular band intensities in the momentt _m after cut-off the pulse. The values oft _m(B³_g)>t _m(C³_u)>t _m(Ar I) decrease with increasing total pressure and increase with growing concentration of N₂ in Ar. In the afterglow period the Ar ₂ ⁺ dissociatively recombine in 5p and 4p Ar states. As a result of radiative transitions the metastable Ar (³P_2,0) atoms are formed which consequently due to collisions with N₂ molecules create electronically excited N₂. With increasing nitrogen concentration this effect becomes less pronounced and at concentration of N₂ greater than 0·5% it is negligible.     

The effect of the rotational excitation of NO on the stereodynamics for the reaction C(~3P)+NO(X~2Π)→CN(X~2Σ~+)+O(~3P)

The stereodynamic properties of the reaction C(3P)+NO(X2Π)→CN(X2Σ+)+O(3P) in different rotational states of reactant NO are studied theoretically by using the quasiclassical trajectory method on 2A' and 2A' potential energy surfaces(PESs) at a collision energy of 0.06 eV.The vector properties in different rotational states on the two surfaces are discussed in detail.The results indicate that the rotational excitation of NO has considerable influence on the stereodynamic property of the reaction occurring on the two surfaces.At the same time,the calculated polarization-dependent differential cross sections(PDDCSs) in different initial rotational states manifest that products are strongly polarized at three scattering angles.     

氧化金激光诱导荧光光谱:b~4Π_(3/2)—X~2Π_(3/2)跃迁

研究Au—O键可以帮助人们更好理解不断发展的金化学科学,而氧化金AuO是含Au—O键最简单的模型,因此对氧化金分子的电子态结构进行研究有重要的科学意义。激光诱导荧光光谱是研究分子结构和化学键的有效手段。利用激光溅射结合超声射流技术产生气相氧化金分子(AuO),采用激光诱导荧光光谱技术测量氧化金在16 500～18 500 cm~(-1)范围内的电子谱。消融激光(Leibao Dawa-300)溅射高纯度(99.9%)金靶产生金原子,将靶材安装在真空步进电机上由步进电机带动转动,保证溅射激光每次打在靶材不同的位置,保证信号的稳定度。高压纯氧气经脉冲阀(Parker, General Valve, series 9)进入真空腔室与金原子反应生成气相氧化金分子AuO。Nd∶YAG激光器(Continuum SureliteⅡ-10)泵浦染料激光器(Sirah, Cobra-Stretch)输出线宽为0.05 cm~(-1)、脉宽为5 ns、能量为0.1 mJ·pulse~(-1)的激光,该激光激发前述产生的氧化金分子至激发态。扫描染料激光器,使用光电倍增管PMT(EMI, ET9202QB)探测此荧光。示波器卡(Picoscope 6404C,500 MHz,14 bits)将光电倍增管探测的信号转换成数字信号输入到计算机,采用基于LabVIEW的分析程序读取信号。分析所测量的光谱,带头在17 152.94, 17 552.17, 17 932.78和18 291.62 cm~(-1)的四个振转谱带被归属为b~4Π_(3/2)(v′=0, 1, 2, 3)-X~2Π_(3/2)(v″=0)跃迁谱。对转动分辨的光谱进行拟合,得到激发态b~4Π_(3/2)态的光谱常数,包括转动常数和离心畸变常数。分析了激发态可能的电子组态,为1σ~21π~41δ~42σ~12π~33σ~(*1)。     

Theoretical prediction of the optimal conditions for observing the stereodynamical vector properties of the C(~3P) + OH(X~2Π) → CO(X~1 Σ~+) + H(~2S) reaction

The best optimal initial reactant state and collision energy for observing the stereodynamical vector properties of the title reaction in the ground electronic state X2A potential energy surface(PES) [Zanchet et al. 2006 J. Phys. Chem. A 110 12017] are theoretically predicted using the quasi-classical trajectory(QCT) method for the first time. The calculated results reveal that the smallest value of the rotational quantum number j, larger vibrational quantum number v, and the lower strength of collision energy should be selected for offering the most obvious picture about the stereodynamical vector properties. Polarization-dependent differential cross sections and the angular momentum alignment distribution, P(θr) and P(Φr) in the center-of-mass frame, are obtained to gain an insight into the alignment and orientation of the product molecules. The rotational angular momentum vector j of CO is aligned to be perpendicular to reagent relative velocity k. The product polarizations align along the y axis, pointing to the positive direction of the y axis. A new method is developed to investigate massive reactions with various initial states and to further study the vector properties of the fundamental reactions in detail.     

Absorption spectra and isotope shifts of the(2, 0),(3, 1), and(8, 5) bands of the A~2Π_u-X~2Σ_g~+ system of ~(15)N_2~+ in near infrared

The high-resolution absorption spectra of the(2, 0),(3, 1), and(8, 5) bands of the A~2Π_u–X~2Σ_g~+system of~(15) N_2~+ have been recorded by using velocity modulation spectroscopy technique in the near infrared region. The rotational constants of the X~2Σ_g~+and A~2Π_u states of~(15) N_2~+ were derived from the spectroscopic data. The isotope shifts of these bands of the A~2Π_u–X~2Σ_g~+system of~(14) N_2~+ and~(15) N_2~+ were also analyzed and discussed.     

Polarization spectroscopy of Na2 A1Σu+-b3Πu ← X1Σg+ intercombination bands

The A¹Σ_u⁺ ∼ b³Π_u perturbation of Na₂ in several high vibrational levels has been studied by polarization spectroscopy. Deperturbed molecular constants are given for the mutually interacting v_A = 26 ∼ v_b = 28 and v_A = 34 ∼ v_b = 34 vibrational levels.     

Interaction of Zn atoms in the 1 S and 3 P states with N2 molecules in the X 1Σ g + and A 3Σ u + states at moderate distances between the atom and molecule

An asymptotic method was used to derive analytical expressions for the matrix elements of interaction between the N₂ molecule in the X ¹Σ _g ⁺ and A ³Σ _u ⁺ electronic states and the Zn atom in the ¹ S and ³ P states. Quadrupole-quadrupole, dispersion, and exchange interactions were taken into consideration. The character of the set of diabatic vibronic potential energy surfaces of the system suggests that the energy transfer in the process N₂(A ³Σ _u ⁺ ) + Zn(¹ S) → N₂(X ¹Σ _g ⁺ ) + Zn(³ P) may prove to be rather effective.     

Lifetimes,population and deactivation mechanisms of theC 1 ∏ u , 23 ∏ g and 21∑ u + states of Na2

The UV and visible fluorescence of Na₂ molecules in a heat-pipe, excited by the frequency doubled radiation of a tunable mode-locked cavity-dumped cw dye laser was observed through a monochromator, using time-resolved single-photon counting. The effective lifetimes of the directly excitedC ¹ _u state and the collisionally populated 2³ _g and 2¹ _u ⁺ states have been measured as a function of sodium-vapor pressure and argon pressure which yields the radiative lifetimes, the population mechanisms and the collisional quenching cross sections of the three states.