激发态RbHe(Ar)分子的光离解

本文研究了Rb（5^2P) He(Ar) nhv→Rb(7^2D) He(Ar) n-1)hv过程，激光频率调离Rb7D5/2→5P3/2跃迁谱线20－100cm^-1，测量了精细结构普线强度分支出I（7D3／2→5P1／2）／I（7D5／2→5P3／2）。测量结果表明，原相互作用势和非绝热效应在分子离解动力学中起关键作用。     

NaK分子激发态的预离解和碰撞激发转移

用Ar+激光器固定频率488.0nm线激发Na-K混合蒸汽,NaK分子激发态通过自发辐射、预离解和与基态原子的碰撞激发转移而去布居,测量在不同K原子密度下原子荧光对分子荧光的强度比,结合NaK(E)态寿命,得到了预离解率和碰撞激发转移率.     

双原子分子离解能的精确研究

基于LeRoy与Bemstein的工作，孙卫国等最近建立了计算精确的双原子分子离解能的新解析表达式．应用该公式和最近建立的研究双原子分子精确振动能谱的代数方法（AM），我们研究了一些双原子分子部分电子态的分子离解能，并与实验值进行了比较．研究结果表明，用新解析式获得的精确分子离解能与实验值符合得非常好．该式在理论上提供了获得精确分子离解能的物理新方法．     

Na2分子部分电子态的完全振动能谱和离解能的精确研究

对于大多数双原子分子的电子态,用现代实验方法或精确的量子理论方法往往可以获得含m个振动能级的能谱子集合[Ev],而不易得到包含最高振动能级在内的所有高振动量子态能级的完全振动能谱{Ev}.鉴于Na2分子电子态的振动能谱和分子离解能De在实际研究和应用中的重要性,使用基于微扰理论的代数方法(AM),获得了Na2分子一些电子态的振动光谱常数和完全振动能谱;使用基于AM的代数能量方法(AEM)获得了这些电子态的正确离解能.研究结果表明:AM方法能从少数精确的实验能级获得精确的分子振动光谱常数集合和正确的完全振动能谱{Ev},AEM方法获得的分子离解能比由文献发表的振动光谱常数计算得到的近似离解能值更准确,对于难以获得分子离解能的那些电子激发态,AEM方法能给出合理的离解能数据.     

双原子分子离解能的精确研究

基于LeRoy与Bernstein的工作,孙卫国等最近建立了计算精确的双原子分子离解能的新解析表达式.应用该公式和最近建立的研究双原子分子精确振动能谱的代数方法(AM),我们研究了一些双原子分子部分电子态的分子离解能,并与实验值进行了比较.研究结果表明,用新解析式获得的精确分子离解能与实验值符合得非常好.该式在理论上提供了获得精确分子离解能的物理新方法.     

Na2分子部分电子态的完全振动能谱和离解能的精确研究

对于大多数双原子分子的电子态，用现代实验方法或精确的量子理论方法往往可以获得含m个振动能级的能谱子集合［Ev］，而不易得到包含最高振动能级在内的所有高振动量子态能级的完全振动能谱{Ev}.鉴于Na2分子电子态的振动能谱和分子离解能De在实际研究和应用中的重要性，使用基于微扰理论的代数方法（AM），获得了Na2分子一些电子态的振动光谱常数和完全振动能谱；使用基于AM的代数能量方法（AEM）获得了这些电子态的正确离解能.研究结果表明：AM方法能从少数精确的实验能级获得精确的分子振动光谱常数集合和正确的完全振动能谱{Ev}，AEM方法获得的分子离解能比由文献发表的振动光谱常数计算得到的近似离解能值更准确，对于难以获得分子离解能的那些电子激发态，AEM方法能给出合理的离解能数据. 关键词： Na2分子 代数方法 振动能级 离解能 电子激发态     

q变形振子模型描述的双原子分子的能级数与离解能

本文利用q变形振子模型,导出了双原子分子的势阱总能级数和离解能公式。实际计算表明,q振子模型计算的离解能,略大于实验值,误差平均约为10％,优于常用的Birge-Sponer外推法,可作为一种估算离解能的新方法。 关键词：     

双原子分子振动能谱与离解能的精确研究

代数方法(AM)的建立解决了实验方法和精确量子力学理论方法难以获得双原子分子的包含最高振动能级在内的所有高阶振动能级的精确数值这一问题.基于LeRoy与Bernstein的工作,孙卫国等又建立了精确计算双原子分子离解能的新解析表达式.应用新公式和代数方法(AM),研究了一些双原子分子部分电子态的振动能谱和分子离解能,获得了与实验值符合非常好的理论结果.该方法在理论上提供了获得双原子分子完全振动能谱和精确分子离解能的物理新方法.     

423—475nm的激光作用下呋喃分子的多光子电离离解研究

在波长为423—475nm的激光作用下对呋喃分子的多光子电离离解过程进行了研究.在此实验波段内,呋喃分子主要经历的是(3+1)多光子过程.得到了呋喃分子的共振多光子电离分质量谱以及离子强度与激光强度的关系.对共振多光子电离谱峰进行了里德堡态标识. 关键词：     

用新公式精确研究N_2分子部分电子态的离解能

本文使用代数方法(AM),研究了N_2分子的X~1∑~+_g、A~3∑~+_u、B~(′3)∑~-_u、a′~1∑~-_u、b′~1∑~+_u、B~3∏_g、c′_4~1∑~+_u等七个电子态的离解能;然后使用新公式计算了这些电子态的离解能,并分别与离解能的实验值进行了分析对比.结果表明:使用新公式得到的分子离解能与离解能的实验值更为接近.对于那些用实验方法还难以获得其离解能的电子态,该式提供了一种获得其离解能的新途径.     

Ab initio calculations of accurate dissociation energy and analytic potential energy function for the second excited state B1∏ of 7LiH

The reasonable dissociation limit of the second excited singlet state B¹∏ of ⁷LiH molecule is obtained. The accurate dissociation energy and equilibrium geometry of the B¹\Pi state are calculated using a symmetry-adapted-cluster configuration--interaction method in full active space. The whole potential energy curve for the B¹∏ state is obtained over the internuclear distance ranging from about 0.10nm to 0.54nm, and has a least-square fit to the analytic Murrell--Sorbie function form. The vertical excitation energy is calculated from the ground state to the B¹∏ state and compared with previous theoretical results. The equilibrium internuclear distance obtained by geometry optimization is found to be quite different from that obtained by single-point energy scanning under the same calculation condition. Based on the analytic potential energy function, the harmonic frequency value of the B¹∏ state is estimated. A comparison of the theoretical calculations of dissociation energies, equilibrium interatomic distances and the analytic potential energy function with those obtained by previous theoretical results clearly shows that the present work is more comprehensive and in better agreement with experiments than previous theories, thus it is an improvement on previous theories.     

Ab initio calculation of accurate dissociation energy, potential energy curve and dipole moment function for the A1∑ + state 7LiH molecule

The reasonable dissociation limit of the A¹∑⁺ state $^{7}$LiH molecule is obtained. The accurate dissociation energy and the equilibrium geometry of this state are calculated using a symmetry-adapted-cluster configuration-interaction method in complete active space for the first time. The whole potential energy curve and the dipole moment function for theA¹∑⁺ state are calculated over a wide internuclear separation range from about 0.1 to 1.4\,nm. The calculated equilibrium geometry and dissociation energy of this potential energy curve are of R_{\e}=0.2487\,nm and D_{\e}=1.064\,eV, respectively. The unusual negative values of the anharmonicity constant and the vibration-rotational coupling constant are of \textit{\omega }_{\e}\textit{\chi }_{\e}=--4.7158cm^{ - 1} and \textit{\alpha }_{\e}=--0.08649cm^{ -1}, respectively. The vertical excitation energy from the ground to the A¹∑⁺ state is calculated and the value is of 3.613\,eV at 0.15875nm (the equilibrium position of the ground state). The highly anomalous shape of this potential energy curve, which is exceptionally flat over a wide radial range around the equilibrium position, is discussed in detail. The harmonic frequency value of 502.47cm¹ about this state is approximately estimated. Careful comparison of the theoretical determinations with those obtained by previous theories about the A¹∑⁺ state dissociation energy clearly shows that the present calculations are much closer to the experiments than previous theories, thus represents an improvement.     

S_2(B~3Σ_u~-→X~3Σ_g~-(ν′≥18,0))弥散谱带的自旋-轨道从头计算

采用从头计算方法从理论上解释了实验中双原子分子S_2(B~3Σ_u~-→X~3Σ_g~-吸收谱中谱带(18,0)开始出现的弥散现象.计算了包含自旋-轨道耦合(SOC)的B3Σu-和排斥的15Πu,23Σu 态的电子势能曲线.对于(18,0)谱带开始弥散,给出了与其他文献不同的物理解释.计算结果表明B3Σu-与15Πu,23Σu 态的SOC作用导致预解离对谱带的弥散起着决定作用,并与实验结果作了比较,符合很好.     

离心压气机转子内部流场S_1／S_2全三元迭代解

为了比较准三元解和全三元解的差异，验证准三元解在计算离心压气机转子内部流场的准确程度，研究离心压气机转子内部流场全三元流动特性，本文对一有激光测量结果的高压比离心压气机［１］叶轮内部流场进行了全三元迭代计算，分析了Ｓ１／Ｓ２两类流面在叶轮通道内分布形态，比较了两类流面准三元解与全三元解的计算结果，讨论了无粘二次流的分布。并进一步和激光测量值及Ｎ－Ｓ三元直接解进行了详细的比较。     

硫化铋微晶掺杂薄膜的制备及光学性能的研究

用溶胶－凝胶法能够有效地制备含０．５％的具有量子尺寸效应的Ｂｉ２Ｓ３微晶掺杂硅薄膜。薄膜的室温透射光谱发现，在５００℃热处理时，随着热处理时间的延长，薄膜的特征透射谱谷会发生向长波方向的移动，作者认为这样的移动于量子尺寸效应。本文还报道了在ＹＡＧ强激光的作用下能够观察到薄膜样品所产生的倍频信号，并讨论了产生倍频的原因。     

S3解离中的非绝热过程

采用量子力学从头计算方法研究了硫的三聚物S_３低激发态解离过程.构造了S_３分子的解离极限.对态态间跃迁极矩的计算表明，在势能曲面的交叉区域态态间存在相互转换的非绝热过程，从而确定了在S_３解离为S₂的复杂过程中，非绝热预解离是重要的解离通道. 关键词： ３')" href="#">S_３ 从头算 预解离 非绝热     

Bound-free transitions and the dissociation limit

Following a sequential two-photon excitation, fluorescence is observed from several selectively excited single rotational-vibrational energy levels of theE ³ π0 _g ⁺ state of molecular iodine. The re-emittedE →B fluorescence spectrum from each of the populated rovibrational level of theE state consists of a series of sharp lines terminating on the various discrete ro-vibrational levels of theB state and a few broad lines due to transitions taking place on to the continuum of theB state. The point of transition from sharp lines to broad features in the fluorescence spectrum has been utilized to determine theB state dissociation limit. This method of obtaining the dissociation limit of the molecular electronic states appears to be quite simple and straightforward.     

SSAr体系的分析势能函数研究

利用ＭＰ２／６－３１＋Ｇ ａｂ ｉｎｉｔｉｏ计算方法优化出出了ＳＳＡｒ体系半弱结合分子的结构参数和离解能,以及它们的谐性力常数。采用多体项展式方法,导出ＳＳＡｒ）Ｘ＾３∑）基态分子的分析势能函数,获得ＳＳＡｒ（Ｘ＾３∑）体系的热能面函数的基本性质,正确地复现出ＳＳＡｒ分子的平衡结构特征,对ＳＳＡｒ体系势能函数进行了研究。     

Spectroscopy and dissociation of sulfuryl halides SO2X2 (X=F,Cl)

The spectroscopy and dissociation of the sulfuryl halides SO₂F₂ and SO₂Cl₂ have been studied in detail using ab initio methods. The possibility of various dissociation channels has been explored taking into account that the fragmented atoms and molecules can stay in their ground state only. An interesting pattern was observed in their dissociation energy spectra for the dissociation channels. The singlet potential energy surfaces for the exit channels of these molecules have been analysed. The release of halogen molecules after dissociation is discussed from an industrial point of view. Finally, the enthalpy of formation of these molecules was computed using the ab initio results. Our results agree very well with the experimental values available.     

Ab initio calculations on the spectroscopic constants, vibrational levels and classical turning points for the 21∏u state of dimer 7Li2

The accurate dissociation energy and harmonic frequency for the highly excited 2^1Пu state of dimer ^7Li2 have been calculated using a symmetry-adapted-cluster configuration-interaction method in complete active space. The calculated results are in excellent agreement with experimental measurements. The potential energy curves at numerous basis sets for this state are obtained over a wide internuclear separation range from about 2.4a0 to 37.0a0. And the conclusion is gained that the basis set 6-311＋＋G（d,p） is a most suitable one. The calculated spectroscopic constants De, Re, ωe, ωeχe, ae and Be at 6-311＋＋G（d,p） are 0.9670 eV, 0.3125 nm, 238.6 cm^-1, 1.3705 cm^-1, 0.0039 cm^-1 and 0.4921 cm^-1, respectively. The vibrational levels are calculated by solving the radial SchrSdinger equation of nuclear motion. A total of 53 vibrational levels are found and reported for the first time. The classical turning points have been computed. Comparing with the measurements, in which only the first nine vibrational levels have been obtained so far, the present calculations are very encouraging. A careful comparison of the present results of the parameters De and We with those obtained from previous theories clearly shows that the present calculations are much closer to the measurements than previous theoretical results, thus representing an improvement on the accuracy of the ab initio calculations of the potentials for this state.