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：     

硫化锂分子的分析势能函数和光谱

应用密度泛函理论的B3LYP方法和6-311++g（d,p）基组,研究Li₂、LiS和Li₂S分子的基态构型.结果表明它们的基电子态分别为X¹Σ_g⁺、X²Π和X¹Σ_g⁺.通过非线性曲线拟合,得到基态LiS和Li₂分子的4参数Murrell-Sorbie分析势能函数,计算它们的光谱参数和力常数.基于多体项展式理论得到了基态Li₂S分子的单重态势能面的分析函数.利用得到的分析势能函数重构基态单重Li₂S分子的旋转图、伸缩图和旋转伸缩图,准确地再现了Li₂S分子的静态特征,如平衡结构,最低能量,合理反应通道.从等值势能面图看出,反应Li+S+Li→Li₂S是一个无阈值反应.S原子攻击Li₂分子的反应通道上,有一个过渡态.Li原子攻击LiS分子通道上也有一个过渡态.     

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.     

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.     

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：     

O_2分子B~3Σ_u~-态势能曲线的从头计算

B~3Σ_u~-态是O_2的最强的三重跃迁(B~3Σ_u~-←XΣ_g~-)Schumann-Runge(SR)带的上态,SR吸收带在保护地球、阻止紫外辐射等方面起着关键作用.SR连续带的光解离是平流层O原子及O_3的主要来源,掌握详细准确的O_2分子的电子态势能曲线,有助于对这些光谱现象的深入理解.本文通过MOLPRO软件,采用包含Davison修正的内收缩的多参考组态相互作用(ic MRCI+Q)方法,对O2的B~3Σ_u~-态的势能曲线进行了计算,采用的多参考组态函数来自完全活性空间自洽场计算.首先,采用共价组态构成多参考组态,对和B~3Σ_u~-态对称性相同的四个态进行了态平均计算,发现B3Σ_u~-态不存在双势阱结构,文献(Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy 2014 124 216)中双势阱的产生是根的振荡(root flipping)造成的,即B~3Σ_u~-态的势能曲线在核间距约为0.2 nm处跳变到能量相近的23?态的势能曲线上.本文中的态平均计算避免了这种根的振荡.接着,采用完全活性空间组态相互作用的方法计算B~3Σ_u~-态的势能曲线,通过改变活性空间的轨道组成,发现带有2π_u轨道电子布居的里德伯组态对B~3Σ_u~-态的束缚态的特征的出现是必不可少的.最后,通过将2π_u轨道加入到活性空间中,实现将相关的里德伯组态加入到多参考组态,对B~3Σ_u~-态的势能曲线进行了icMRCI+Q计算,得到相较于以往的理论计算与实验值更加相近的势能曲线以及光谱常数.本文探讨里德伯组态贡献的过程为如何确定多参考组态相互作用计算中的参考组态、提高理论计算的准确度提供了可以借鉴的途径.     

超冷铯分子0u+(6P3/2)长程态的高灵敏光缔合光谱研究

利用发展的调制俘获损耗荧光光谱技术实验测量了超冷铯分子0_u⁺(6P_3/2)长程态的高灵敏光缔合光谱. 光谱探测范围较国际已有报道扩大了60 cm^-1, 观察到25个长程区域新的振动能级. 通过LeRoy-Bernstein公式对振动束缚能数据进行拟合, 获得了超冷铯分子0_u⁺(6P_3/2)态的长程系数C₃ 为16.103±0.010. 构建了超冷铯分子0_u⁺(6P_3/2)态长程区域的势能曲线.     

大气压空气纳秒脉冲阵列式线-线SDBD等离子体的电学及发射光谱特性研究

提出了一种阵列式线-线沿面介质阻挡放电结构,利用双极性高压纳秒脉冲电源,在大气压空气中激励产生了相对大面积的放电等离子体。其中,高压电极、地电极均为圆柱形金属,放电反应器由20组相间排列的阵列式线型高压电极和套有介质管的阵列式线型地电极组成。利用电压探头、电流探头、示波器等测量了放电电压和放电总电流,并计算得出了放电的实际电流。利用光纤、光栅光谱仪、CCD等测量了波长范围在300～440 nm和766～778 nm的发射光谱,即氮分子第二正带N₂ (C3Π_u→B3Π_g)包括Δν= +1, 0, -1, -2, -3、氮分子离子第一负带N+₂(B2Σ+_u→X2Σ+_g),N₂ (B3Π_g→A3Σ+_u)和O (3p5P→3s5S₂)的发射光谱。比较了氮分子第二正带N₂ (C3Π_u→B3Π_g)的各个振动峰和各个活性物种的发射光谱强度,以及这些发射光谱强度随着脉冲峰值电压的变化。测量了N₂(C3Π_u→B3Π_g, 0-0)的二次、三次衍射光谱,与原始光谱在转动带、背景光谱等方面进行了比较,并计算了二次衍射和原始光谱之间的峰值比。利用氮分子第二正带N₂ (C3Π_u→B3Π_g, Δν=+1, 0, -1, -2)和氮分子离子第一负带N+₂ (B2Σ+_u→X2Σ+_g, 0-0)模拟了等离子体的转动温度和振动温度,对模拟结果进行了比较,并研究了脉冲峰值电压对等离子体振动温度和转动温度的影响。通过测量放电的电压和计算得到的放电电流发现,当脉冲峰值电压为22 kV,脉冲重复频率为150 Hz时,阵列式线-线沿面介质阻挡放电的放电电流在正脉冲、负脉冲两个方向上均可达75 A左右。通过诊断放电等离子体的发射光谱发现,在测量的波长范围内,放电产生的活性物种主要有氮分子第二正带N₂ (C3Π_u→B3Π_g)、氮分子离子第一负带N+₂(B2Σ+_u→X2Σ+_g),N₂ (B3Π_g→A3Σ+_u)和O (3p5P→3s5S₂)。在脉冲峰值电压22～36 kV的变化范围内,氮分子第二正带N₂(C3Π_u→B3Π_g, 0-0)的发射光谱强度始终保持最强,N₂ (B3Π_g→A3Σ+_u)次之,而氮分子离子第一负带N+₂(B2Σ+_u→X2Σ+_g)和O (3p5P→3s5S₂)的发射光谱强度较弱。同时,当脉冲峰值电压升高时,氮分子第二正带N₂ (C3Π_u→B3Π_g)的所有振动峰,以及氮分子离子第一负带N+₂(B2Σ+_u→X2Σ+_g),N₂ (B3Π_g→A3Σ+_u)和O (3p5P→3s5S₂)的发射光谱强度均随之升高。通过比较氮分子第二正带N₂(C3Π_u→B3Π_g, 0-0)的原始、二次衍射、三次衍射光谱发现,二次、三次衍射光谱的转动带更清晰,但三次衍射光谱的背景更强,因此氮分子第二正带N₂(C3Π_u→B3Π_g)的二次衍射光谱更有利于模拟等离子体的转动温度。通过比较模拟得到的振动温度和转动温度发现,氮分子第二正带N₂ (C3Π_u→B3Π_g, Δν=-2)在N₂ (C3Π_u→B3Π_g)四个谱带Δν=+1, 0, -1, -2中最适于模拟等离子体振动温度,而利用氮分子离子第一负带N+₂ (B2Σ+_u→X2Σ+_g,0-0)模拟得到的等离子体转动温度要比N₂ (C3Π_u→B3Π_g, Δν=-2)的模拟结果高约10～15 K。同时,当脉冲峰值电压升高时,由N₂ (C3Π_u→B3Π_g, Δν=-2)和N+₂ (B2Σ+_u→X2Σ+_g, 0-0)模拟得到等离子体的转动温度均出现了略微上升的趋势,而利用N₂ (C3Π_u→B3Π_g, Δν=-2)模拟得出的振动温度则略微下降。     

Theoretical Study on the Low-Lying Electronic States of He2, He2+, and He2++

The equilibrium geometries, potential energy curves, spectroscopic dissociation energies of the ground and low-lying electronic states of He₂, He₂⁺ and He₂⁺⁺ are calculated using symmetry adapted cluster/symmetry adapted cluster-configuration interaction (SAC/SAC-CI) method with the basis sets CC-PV5Z. The corresponding dissociation limits for all states are derived based on atomic and molecular reaction statics. The analytical potential energy functions of these states are fitted with Murrell--Sorbie potential energy function from our calculation results. The spectroscopic constants B_e, α _e, ω _e, and ω _e χ _e of these states are calculated through the relationship between spectroscopic data and analytical energy function, which are in well agreement with the experimental data. In addition, the origin of the energy barrier in the ground state X¹Σ_g⁺ of He₂⁺⁺ energy curve are explained using the avoided crossing rules of valence bond model.     

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.     

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.     

Photoassociation spectra of ultracold ~(85)Rb_2 molecule in 0_u~+ long range state near the 5S_(1/2)+ 5P_(1/2) asymptote

We investigate the high resolution photoassociation spectra of ~(85)Rb_2 molecules in 0~+_u long range state below the(5S_(1/2)+ 5P_(1/2)) asymptote. The ~(85)Rb atomic samples are trapped in a dark magneto–optical trap(MOT) and prepared in the dark state. With the help of trap loss technique, we obtain considerable photoassociation spectroscopy with rovibrational resolution, some of which have never been observed before. The observed spectrum is fitted by a rigid rotation model, and the rotational constants of ultracold ~(85)Rb_2 molecule in long range 0~+_u are obtained for different vibrational states. By applying the Le Roy–Bernstein method, we assign the vibrational quantum numbers and derive C_3 coefficient, which is used to obtain the potential energy curve.     

Configuration interaction studies on the spectroscopic properties of PbO including spin-orbit coupling

Lead oxide(Pb O), which plays the key roles in a range of research fields, has received a great deal of attention. Owing to the large density of electronic states and heavy atom Pb including in Pb O, the excited states of the molecule have not been well studied. In this work, high level multireference configuration interaction calculations on the low-lying states of Pb O have been carried out by utilizing the relativistic effective core potential. The effects of the core-valence correlation correction, the Davidson modification, and the spin–orbital coupling on the electronic structure of the Pb O molecule are estimated. The potential energy curves of 18 Λ-S states correlated to the lowest dissociation limit(Pb(~3P_g) + O(~3P_g)) are reported. The calculated spectroscopic parameters of the electronic states below 30000 cm~(-1), for instance, X~1Σ~+, 1~3Σ~+,and 1~3Σ~-, and their spin–orbit coupling interaction, are compared with the experimental results, and good agreements are derived. The dipole moments of the 18 Λ-S states are computed with the configuration interaction method, and the calculated dipole moments of X~1Σ~+and 1~3Σ~+are consistent with the previous experimental results. The transition dipole moments from 1~1Π, 2~1Π, and 2~Σ to X~1Σ~+and other singlet excited states are estimated. The radiative lifetime of several low-lying vibrational levels of 1~1Π, 2~1Π, and 2~1Σ~+ states are evaluated.     

用于α和μ常数变化测量的碘离子光谱研究

分子离子I_2~+的禁戒跃迁光谱有可能用于测量α和μ常数的变化,并且具有增强的灵敏度.通过分析I_2~+在11860—13100 cm~(-1)范围内的转动光谱,拟合了A~2Π_(3/2)-X~2Π_(3/2)系统31个振转带的5759根吸收谱线,得到5个属于X~2Π_(3/2)态和9个属于A~2Π_(3/2)态的振动能级准确的转动光谱常数.在量子噪声极限和1 Hz跃迁线宽的条件下,计算得到X~2Π_(3/2)和X~2Π_(1/2)之间的禁戒跃迁对α和μ常数变化测量的灵敏度为δ_(α/α)≈2.37×10~(-19)a~(-1)和δ_(μ/μ)≈1.18×10~(-18)a~(-1).     

超短脉冲激光烧蚀石墨产生的喷射物的时间分辨发射光谱研究

本文使用不同激光能流(18 J/cm²–115 J/cm²)和脉冲宽度(50 fs–4 ps)的超短脉冲激光在真空中(4×10^-4 Pa)烧蚀高定向热解石墨. 通过测量烧蚀喷射物的时间分辨发射光谱研究喷射物的超快时间演化. 在喷射物发射光谱中, 观察到了C₂基团的天鹅带光谱系统, 416 nm附近C₁₅基团的由电子能级¹Σ_u⁺ 和¹Σ_g⁺之间的振动跃迁产生的光谱峰以及连续谱. 50 fs, 115 J/cm²的脉冲激光烧蚀产生的喷射物的连续谱的强度衰减分为快速下降和慢速下降两个阶段(以20 ns时间延迟为分界). 这表明连续谱是由两种不同的组分贡献的. 快速下降阶段, 连续谱主要由碳等离子体通过韧致辐射产生; 慢速下降阶段, 连续谱主要由烧蚀后期产生的大颗粒碳簇的热辐射贡献. 实验结果还揭示了激光能流的提高, 会明显增加喷射物中碳等离子体和激发态C₂的含量, 但对质量稍大的C₁₅的影响较小; 此外, 50 fs脉冲激光烧蚀产生的连续谱的存在时间会随着激光能流的减小而增大, 这说明低能流更有利于在烧蚀后期产生碳簇. 脉宽主要影响喷射物连续谱的时间演化. 4 ps脉冲激光烧蚀产生的连续谱的整个时间演化过程明显慢于50 fs脉冲产生的连续谱.     

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.     

SiCl自由基X2Π和A2Σ+态的光谱性质

采用内收缩多参考组态相互作用(ic MRCI)方法结合Dunning等相关一致基,计算Si Cl自由基X²Π和A²Σ⁺态的势能曲线.讨论参考能和相关能外推对X²Π和A²Σ⁺态光谱的影响.对势能进行相对论修正及核价修正计算.拟合势能曲线得到X²Π和A²Σ⁺态的光谱常数.它们与实验结果一致.利用Breit-Pauli算符,计算旋轨耦合效应,得到X²Π_1/2和X²Π_3/2的势能曲线、并计算它们的光谱常数.求解双原子分子核运动的径向SchrÖdinger方程,获得无转动SiCl自由基2个Λ-S态及X²Π态的耦合分裂态的全部振动态.得到J=0时X²Π态的自旋-轨道耦合常数、较高振动态的惯性转动常数以及X²Π_1/2和X²Π_3/2的振动能级等分子常数.     

Low-lying electronic states of CuN calculated by MRCI method

The high accuracy ab initio calculation method of multi-reference configuration interaction(MRCI) is used to compute the low-lying eight electronic states of CuN.The potential energy curves(PECs) of the X~3∑~-,1~3Π,2~3∑~-,1~3△,1~1△,1~1∑~-,1~1Π,and ~5∑~- in a range of R=0.1 nm-0.5 nm are obtained and they are goodly asymptotes to the Cu(~2S_g) + N(~4S_u) and Cu(~2S_g)+N(~2D_u) dissociation limits.All the possible vibrational levels,rotational constants,and spectral constants for the six bound states of X~3∑~-,1~3Π,2~3∑~-,1~1△,1~1∑~-,and 1~1 Π are obtained by solving the radial Schrdinger equation of nuclear motion with the Le Roy provided Level 8.0 program.Also the transition dipole moments from the ground state X~3∑~- to the excited states 1~3Π and 2~3∑~- are calculated and the result indicates that the 2~3∑-X~3∑ transition has a much higher transition dipole moment than the 1~3Π-X~3∑~- transition even though the l~3Π state is much lower in energy than the 2~3∑~- state.     

激光冷却OH分子的理论研究

采用高精度的多参考组态相互作用方法计算OH分子基态和第一激发态的势能曲线.为获得更精确的计算结果,在计算过程中考虑Davidson修正、标量相对论效应、核价相关效应和自旋轨道耦合效应.基于计算的Λ-S和?态的势能曲线,对一维径向薛定谔方程进行数值求解,得到各个电子态的光谱数据,与已报道的实验值和理论值相符合.获得OH分子的永久偶极矩、跃迁偶极矩、振动能级、Franck-Condon因子及辐射寿命,结果表明,A~2Σ~+→X~2Π跃迁具有高度对角化的Franck-Condon因子(0.9053)和短的辐射寿命(5.8363×10~(-7)s),符合激光冷却分子的条件.制定了激光冷却OH分子的具体方案,计算得到激光冷却跃迁A~2Σ~+→X~2Π所需的三束激光波长,主光束波长为307.1532 nm,两束重抽运激光波长为344.9163和349.7659 nm.计算结果为超冷OH分子的实验制备提供重要的理论依据.     

LiCl~–阴离子的光谱性质和跃迁性质

采用多参考组态相互作用方法结合全电子基组计算了LiCl~-阴离子5个电子态(X~2Σ~+,A~2Π,B~2Σ~+,3~2Σ~+,2~2Π)的电子结构.为了得到精确的光谱常数,计算中考虑了Davidson修正、芯-价电子关联效应和自旋-轨道稱合效应.拟合得到各电子态的光谱常数、分子常数、自发辐射速率和自发辐射寿命.基态的光谱常数与实验值和其他理论值符合较好,同时报道了LiCl~-阴离子激发态的光谱常数以及其到基态的跃迁性质.计算结果表明A~2Π?X~2Σ~+跃迁具有高对角分布的弗兰克-康登因子f₀₀,第一激发态A~2Π有较短的自发辐射寿命.构造A~2Π(v’)? X~2Σ~+(v")准循环跃迁进行激光冷却LiCl~-阴离子需要一束主激光和两束抽运激光.以上结果预测了激光冷却LiCl~-阴离子是可行的.