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.     

Highly accurate theoretical study on spectroscopic properties of SH including spin–orbit coupling

The multi-reference configuration interaction method plus Davidson correction(MRCI+Q) are adopted to study the low-lying states of SH with consideration of scalar relativistic effect, core-valence(CV) electron correlation, and spin–orbit coupling(SOC) effect. The SOC effect on the low-lying states is considered by utilizing the full Breit–Pauli operator. The potential energy curves(PECs) of 10 Λ–S states and 18 ? states are calculated. The dipole moments of 10 Λ–S states are calculated, and the variation along the internuclear distance is explained by the electronic configurations. With the help of calculated SO matrix elements, the possible predissociation channels of A~2Σ+, c4Σ-and F~2Σ-are discussed. The Franck–Condon factors of A~2Σ~+–X~2Π, F~2Σ~-–X~2Π and E~2Σ~+–X~2Π transitions are determined, and the radiative lifetimes of A~2Σ+and F~2Σ-states are evaluated, which are in good agreement with previous experimental results.     

Theoretical study of spin-forbidden cooling transitions of indium hydride using ab initio methods

The feasibility of spin-forbidden cooling of the In H molecule is investigated based on ab initio quantum chemistry calculations. The potential energy curves for the X~1Σ_(0~+)~+, a~3Π_~(0~-), a~3Π_(0~+), a~3Π_1, a~3Π_2, A~1Π_1, 1~3Σ_(0~-)~+, and 1~3Σ_1~+states of In H are obtained based on multi-reference configuration interaction plus the Davidson corrections method. The calculated spectroscopic constants are in good agreement with the available experimental data. In addition, the influences of the active space and spin–orbit coupling effects on the potential energy curves and spectroscopic constants are also studied. For Re of a~3Π_(0~-), a~3Π_(0~+), a~3Π_1, and a~3Π_2 states, the error from large active space is small. The potential energy curve of the A~1Π_1state is not smooth for small active space. The spin–orbit coupling effects have great influences on the potential well depth and equilibrium internuclear distance of the A~1Π state. The Franck–Condon factors and radiative lifetimes are obtained on the basis of the transition dipole moments of the a~3Π_(0~+) → X~1Σ_(0~+)~+, a~3Π_1 → X~1Σ_(0~+)~+, and A~1Π_1 → X~1Σ_(0~+)~+ transitions. Our calculation indicates that the a~3Π_1( ν'= 0) → X~1Σ_(0~+)~+(ν = 0) transition provides a highly diagonally distributed Franck–Condon factor and a short radiative lifetime for the a3Π1 state, which can ensure rapid and efficient laser cooling of In H.The proposed laser drives a~3Π_1 → X~1Σ_(0~+)~+ transitions by using three wavelengths.     

Differential cross sections for electron impact excitation of molecular hydrogen using the momentum-space multichannel optical method

In the present work, the momentum-space multichannel optical method is employed in four-state close-coupling calculations to study the electronic excitation of H_2 molecules by electron-impact. Particularly, differential cross sections for the X~1Σ_g~+→ b~3Σ_u~+, X~1Σ_g~+→ aΣ_g~+, and X~1Σ_g~+→ c~3Π_u transitions are reported. Comparison is made with the available experimental and theoretical results.     

Factors affecting improvement of fluorescence intensity of quartet and doublet state of NO diatomic molecule excited by glow discharge

We report on the observation of new fluorescence emission spectral transitions obtained from NO diatomic molecule in the region from ultraviolet(UV) to near infrared(NIR) in a low power glow discharge system. This glow discharge electronic excitation populates different quartet and doublet states of NO in its proximity such as the A~2-Σ(υ = 2), b~4Σ(υ = 3), B~2Π(υ = 4), and X~2Π(υ = 33–32) states. Due to inter-system crossing, emission lines originating from these levels to lower lying states are recorded and spectral line assignments are performed. The observed systems include b~4-Σ–a~4Π, B~2Π–a~4Π, a~4Π–X~2Π, A~2Σ–X~2Π, X~2Π–X~2Π(33–15), X~2Π–X~2Π(33–17), X~2Π–X~2Π(33–20), and X~2Π–X~2Π(33–18). This new information will conduce to the better understanding of the interesting features of NO molecule. Such parameters that affect the recording of low density of NO molecules are also discussed In addition to the factors such as the time evolution, argon gas concentration relative to NO mixture, the percentage of NO molecular gas concentration,discharge electric current signals and discharge applied voltage are studied. Those factors would enhance the fluorescence signal intensity of NO molecules. The recent results might be significant as reference data for optimizing the glow discharge spectrometer and diagnostics of NO gas.     

Strong-Field-Induced N_2~+ Air Lasing in Nitrogen Glow Discharge Plasma

We investigate N_2~+ air lasing at 391 nm,induced by strong laser fields in a nitrogen glow discharge plasma.We generate forward N_2~+ air lasing on the B~2Σ_u~+(v'=0)-X~2Σ_g~+(v"=0) transition at 391 nm by irradiating an intense 35-fs,800-nm laser in a pure nitrogen gas,finding that the 391-nm lasing quenches when the nitrogen gas is electrically discharged.In contrast,the 391-nm fluorescence measured from the side of the laser beam is strongly enhanced,demonstrating that this discharge promotes the population in the B~2Σ_u~+(v'=0) state.By comparing the lasing and fluorescence spectra of the nitrogen gas obtained in the discharged and laser-induced plasma,we show that the quenching of N_2~+ lasing is caused by the efficient suppression of population inversion between the B~2Σ_u~+ and X~2Σ_g~+ states of N_2~+,in which a much higher population occurs in the X~2Σ_g~+ state in the discharge plasma.Our results clarify the important role of population inversion in generating N_2~+ air lasing,and also indicate the potential for the enhancement of N_2~+ lasing via further manipulation of the population in the X~2Σ_g~+ state in the discharged medium.     

BaF radical: A promising candidate for laser cooling and magneto-optical trapping

Recently, there have been great interest and advancement in the field of laser cooling and magneto-optical trapping of molecules. The rich internal structure of molecules naturally lends themselves to extensive and exciting applications. In this paper, the radical~(138)Ba~(19) F, as a promising candidate for laser cooling and magneto-optical trapping, is discussed in detail.The highly diagonal Franck–Condon factors between the X~2Σ~+_(1/2)and A~2Π_(1/2) states are first confirmed with three different methods. Afterwards, with the effective Hamiltonian approach and irreducible tensor theory, the hyperfine structure of the X~2Σ~+_(1/2)state is calculated accurately. A scheme for laser cooling is given clearly. Besides, the Zeeman effects of the upper(A~2Π_(1/2)) and lower(X~2Σ~+_(1/2)) levels are also studied, and their respective g factors are obtained under a weak magnetic field.Its large g factor of the upper state A~2Π_(1/2) is advantageous for magneto-optical trapping. Finally, by studying Stark effect of Ba F in the X~2Σ~+_(1/2), we investigate the dependence of the internal effective electric field on the applied electric field. It is suggested that such a laser-cooled Ba F is also a promising candidate for precision measurement of electron electric dipole moment.     

Energy and rotation-dependent stereodynamics of H(~2S) + NH(a~1?) → H_2(X~1Σ_g~+) + N(~2D) reaction

Quasi-classical trajectory calculations are performed to study the stereodynamics of the H(~2S) + NH(a~1?) →H_2(X~1Σ_g~+) + N(~2D) reaction based on the first excited state NH_2(1~2A') potential energy surface reported by Li et al.[Li Y Q and Varandas A J C 2010 J. Phys. Chem. A 114 9644] for the first time. We observe the changes of differential cross-sections at different collision energies and different initial reagent rotational excitations. The influence of collision energy on the k–k' distribution can be attributed to a purely impulsive effect. Initial reagent rotational excitation transforms the reaction mechanism from insertion to abstraction. The effect of initial reagent rotational excitations on k–k' distribution can be explained by the rotational excitation enlarging the rotational rate of reagent NH in the entrance channel to reduce the probability of collision between incidence H atom and H atom of target molecular. We also investigate the changes of vector correlations and find that the rotational angular momentum vector j' of the product H_2 is not only aligned, but also oriented along the y axis. The alignment parameter, the disposal of total angular momentum and the reaction mechanism are all analyzed carefully to explain the polarization behavior of the product rotational angular moment.     

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.     

Potential energy curves,transition dipole moments,and radiative lifetimes of KBe molecule

An ab initio calculations on the ground and low-lying excited states(X~2Σ+, 2~2Σ+, 3~2Σ+, 1~4Π, 2~4Π, 1~4Σ~+, 2~4Σ~+,and 3~4Σ~+) of KBe molecule have been performed using multireference configuration interaction(MRCI) plus Davidson corrections(MRCI+Q) approach with all electron basis set aug-cc-p CV5Z-DK for Be and def2-AQZVPP-JKFI for K.The 3~2Σ+, 1~4Π, 2~4Π, 1~4Σ~+, 2~4Σ~+, and 3~4Σ~+states are investigated for the first time. Inner shell electron correlations are computed on the potential energy curves(PECs) calculations. The spectroscopic and molecular parameters are also predicted. In addition, The transition properties including transition dipole moment, Franck–Condon factors qv'v', Einstein coefficients Av'v', and the radiative lifetimes τυ for the 2~2Σ~+–X~2Σ~+, 3~2Σ~+–X~2Σ~+, and 2~4Π–1~4Π transitions are predicted at the same time.     

AlH~+离子5个Λ-S态和10个?态的光谱性质以及激光冷却的理论研究

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-ccpV6Z计算了AlH~+离子前两个离解极限对应的5个Λ-S态和10个?态的势能曲线.为了提高势能曲线的可靠性和精确性,计算中考虑了自旋轨道耦合效应、芯电子价电子相关和标量相对论修正以及将势能外推至完全基组极限.基于得到的势能曲线,获得了束缚和准束缚的4个Λ-S态和8个?态的光谱常数和振动能级,与已有的实验结果符合.计算了2(1/2)→X~2Σ_(1/2)~+和A~2Π_(3/2)→X~2Σ_(1/2)~+跃迁的跃迁偶极距.利用计算的精确的势能曲线和跃迁偶极矩,获得了2(1/2)~(第一势阱)(υ′=0, 1)→X~2Σ_(1/2)~+(υ′′)和A~2Π_(3/2)(υ′=0, 1)→X~2Σ_(1/2)~+(υ′′)跃迁的高度对角化分布的Franck-Condon因子(f_(00)和f_(11))和大的振动分支比;预测了2(1/2)~(第一势阱)(υ′=0, 1)和A~2Π_(3/2)(υ′=0, 1)态短的自发辐射寿命和窄的辐射宽度,这适合于AlH~+离子的快速激光致冷.所需的3束激光冷却波长都在紫外区域.这些结果表明了激光冷却AlH~+离子的可行性.此外,评估了自旋轨道耦合效应对光谱常数、振动能级和激光冷却AlH~+离子的影响.     

BH~+离子基态及激发态的势能曲线和跃迁性质的研究

利用高精度的多组态相互作用及Davidson修正方法 (MRCI+Q),采用ACV5Z-DK全电子基组计算了BH~+离子的前4个离解通道B~+(~1S_g)+H(~2S_g),B~+(~3Pu)+H(~2S_g),B(~2P_u)+H~+(~1Sg)和B~+(~1Pu)+H(~2Sg)的9个Λ—S态的势能曲线.X~2Σ~+,A~2Π和B~2Σ~+态的光谱常数和已有实验值符合得很好,其中b~4Σ~+,3~2Σ~+,3~2Π和4~2Σ~+态的光谱常数为首次报道,3~2Π和4~2Σ~+态具有双势阱结构.预测了A~2Π和B~2Σ~+态的辐射寿命:τ(A~2Π)=239.2 ns和τ(B~2Σ~+)=431.2 ns.最后在考虑自旋轨道耦合效应下讨论了B~2Σ~+与A~2Π态的势能曲线的相交对激光冷却BH~+离子的影响.     

Na_2~+离子较低电子态势能曲线和光谱常数的理论研究

通过多组态相互作用方法,结合原子有效芯势与极化势,利用非收缩的高斯基函数,计算了Na_2~+分子对应最低9个解离限的36个电子态的势能曲线.基于计算获得的束缚态势能曲线,拟合给出了相应的光谱常数,并与已有的实验和理论结果进行了比较.同时,给出了部分电子态的振动-转动能级和一些同类态避免交叉点的信息.计算获得的光谱信息对冷原子分子光谱与动力学的研究具有参考价值.     

Cl2+离子R支跃迁光谱的理论研究

从双原子分子能级的物理表达式出发进行多次微分,建立了预测双原子分子体系R支高振转跃迁谱线的新解析公式. 使用新解析公式预测双原子体系R支高阶跃迁谱线的数据时,最多只需15条精确的实验跃迁谱线和该跃迁带中对应的上下 振动态的转动光谱常数B′_v 和 B″_v.将该解析公式用于预测Cl₂⁺ 离子 A²∏_u---X²∏_g跃迁系(3,7)带和(4,8)带的跃迁谱线,不仅精确的重复了实验给出的较低阶的跃迁光谱数据值, 而且正确预言了所研究体系中缺失的振转跃迁谱线,尤其是高阶的跃迁谱线数据.     

CHClF2在强红外激光作用下C2*d3Пg态的形成机制

用TEACO₂激光辐照CHCIF₂分子生成电子激发态C₂^*自由基,观察到斯旺带系的六个谱带。本文根据C₂分子态位能曲线的特点,提出C₂^*d³Π_g态的形成机制。C₂是少数较特殊的分子之一,其激发态b³Σ_g^-与第一激发态a关键词：     

K2分子23∏g—13∑u+漫射谱强度的碰撞诱导增强效应

用4415.6?CW激光线获得了5730?附近的K₂分子2³∏_g—1³∑_u⁺漫射荧光谱。实验研究了缓冲气体Ar气压强P对漫射谱峰值强度I_diff的碰撞诱导增强效应。用稳态碰撞模型描述了C¹∏_u—2³∏_g间的能量转移过程,推导出了I_diff-P函数关系,对实验数据进行了令人满意的拟合。这种拟合表明:适当变更实验装置,利用本文模型可以得到C¹∏_u—2³∏_g间的能级交叉速率和碰撞诱导转移速率。 关键词：     

GeS分子基态和低激发态的势能曲线与光谱性质

本文以aug-cc-pv5Z为基组, 采用考虑Davidson修正的多参考组态相互作用方法(MRCI+Q)得到了GeS分子基态(X¹Σ⁺)和5个低激发态(1¹Σ, 1¹Δ, A¹Π, 1⁵Σ⁺, 2⁵Σ⁺)的势能曲线. 计算结果表明: 2⁵Σ⁺态为排斥态, 其余5个态为束缚态; 6个态有着共同的离解通道, 离解极限均为Ge(³P)+S(³P). 利用计算得到的势能曲线得了X¹Σ⁺, 1¹Σ^-, 1¹Δ, A¹Π和1⁵Σ⁺态的垂直跃迁能T_e, 平衡键长R_e, 离解能D_e, 谐振频率ω_e, 非谐性常数ω_ex_e及平衡位置的电偶极矩. X¹Σ⁺态的R_e 为2.034 Å, D_e 为5.728 eV, ω_e为571.73 cm^-1, ω_ex_e为1.6816 cm^-1, 平衡位置的电偶极矩为1.9593 Debye. 激发态1¹Σ, 1¹Δ, A¹Π, 1⁵Σ⁺的T_e 依次为25904.81, 26209.22, 32601.19, 43770.26 cm^-1; R_e依次为2.313, 2.322, 2.188, 2.8790 Å; D_e依次为2.524, 2.487, 1.694, 0.3036 eV, ω_e依次为358.90, 353.08, 376.32, 134.96 cm^-1; ω_ex_e依次为1.2421, 1.2151, 1.6608, 1.9095 cm^-1; 平衡位置的电偶极矩依次为1.3178, 1.4719, 1.5917, -1.9785 Debye. 通过求解核运动的薛定谔方程得到了J=0时X¹Σ⁺, 1¹Σ^-, 1¹Δ, A¹Π和1⁵Σ⁺态前30个振动态的振动能级G_v和分子常数B_v, 得到的结果和已有的实验值及其他理论值符合较好.     

~6Li~(32)S双原子分子的光谱和辐射跃迁理论研究

在aug-cc-pV5Z/CASSCF/MRCI水平上讨论了~6Li~(32)S双原子分子的9个较低能量电子态(X~2∏,a~4△,B~2△,b~4△,A~2∑~+,C~2∏,F~2∑~-,E~2∑~+和D~2∏)的势能函数和光谱常数;其中基态平衡核间距、谐振频率、转动常数等均与实验值相符;b~4∏,C~2∏,D~2∏态的平衡核间距均超过了0.4 nm,并且离解能较小,不稳定.D~2∏态是离子对态,离解极限为Li~+(~1S_g)+S~-(~1S_g).预测了最低激发态A~2∑~+跃迁到基态X~2∏的电子跃迁偶极矩、爱因斯坦自发发射系数、弗兰克-康登因子和辐射寿命.