HeICl络合物的振动预离解：含时黄金规则波包研究

用含时黄金规则波包法计算了ＨｅＩＣｌｖａｎ ｄｅｒ Ｗａａｌｓ络合物分子的振动了解寿命和离解碎片ＩＣｌ的终转动态分布。并与实验和其他理论计算帮了比较。波包计算所用的总传播时间实际上是解离碎片在振动退激发绝热势能面上的滞留时间。终态相互作用对终转动态分布起着决定性作用。并预言了ＨｅＩＣｌ终转动态分布对振动态的依赖。     

利用半经典微扰理论研究H－H_2O的非弹性碰撞—H_2O的转动、振动激发

利用半经典微扰理论计算了在Ｈ－Ｈ２Ｏ的非弹性碰撞中的Ｈ２Ｏ分子的转动、振动激发，并将计算结果与实验结果进行比较。计算中采用了Ｓｃｈａｔｚ和Ｅｌｇｅｒｓｍａ的半经验势能面，水分子的势函数，包括了谐振和非谐振力函数，在考虑了振动和转动耦合的情况下，通过半经典微扰理论来确定水分子末态的振动量子数。在Ｌｏｖｅｊｏｙ等人最近进行的实验中，当热氢原子入射时，水分子的转动和振动被激发了，而且发现水分子的转动角动量有垂直于水分子平面优先激发的趋势。我们的计算也得到出了相同的结果。     

H2O的光解离：单分子解离的出色例子

利用氢原子里德堡态标记的时间飞渡技术研究了Ｈ２Ｏ在１２１和１５７ｎｍ的光解离，并测量出了这两个波长下的ＯＨ产物的振动和转动态分布。实验结果表明，１２１ｎｍ下Ｈ２Ｏ光解离主要产生高转动激发的ＯＨ只有很少振动激发。而在１５７ｎｍ的光解产生ＯＨ的振动激发只有很少转动激发。研究表明高振动激发ＯＨ（ｖ≥２）的相对布居在ＬＩＦ测量的工作中被严重低估了，因此指出ＬＩＦ技术定量测量产物ＯＨ的振动态分布是有问题的。     

利用半经典微扰理论研究H—H2O的非弹性碰撞—H2O的转动,振动…

利用半经典微扰理论计算了Ｈ－Ｈ２Ｏ的非弹性碰撞中的Ｈ２Ｏ分子的转动，振动激发，并将计算结果与实验结果进行了比较。计算中采用了Ｓｃｈａｔｚ和Ｅｌｇｅｒｓｍａ的半经验势能面，水分子的势函数，包括了谐振和非谐振力函数，在考虑了振动和转动耦合的情况焉，通过半经典微扰理论来确定水分子末态的振动量子数。     

反应物分子初始振动激发对O+HCl→OH+Cl反应的立体动力学性质的影响

在Peterson的高精度从头计算势能面上,运用准经典轨线方法讨论了反应物分子初始振动激发对O+HCl→OH+Cl反应的立体动力学性质的影响.反映两矢量k-j′相关的P(θr)函数的分布说明产物的转动角动量j′在垂直于反应物相对速度矢量k的方向上的排列取向程度随着初始反应物振动量子数的增加而增加;反映三矢量k-k′-j′相关的极角分布函数P(r)显示产物的转动角动量有比较弱的定向效应,且随着初始振动量子数的增加,这种弱的定向效应由沿Y轴负向变为沿Y轴正向.说明反应物分子的初始振动激发有利于增强产物分子的转动排列取向效应,但对产物分子P(r)分布的影响则不明显.     

金属镍吸附氢同位素的量子力学计算

根据原子分子反应静力学与群论，确定了ＮｉＨ、ＮｉＤ和ＮｉＴ的基电子状态为２Σ＋。应用基函数６－３１１Ｇ和组态相关ＣＩ或ＱＣＩＳＤ方法，计算了氢同位素分子及其镍化物的能量Ｅ、定容热容Ｃｖ和熵Ｓ。设用总能量中的电子和振动能量近似代表ＮｉＨ、ＮｉＤ和ＮｉＴ分子处于固态时的能量，用总熵中的电子和振动熵近似代表这些分子处于固态时的熵，进而计算了镍吸附Ｈ２、Ｄ２和Ｔ２分子过程的ΔＨ°、ΔＳ°、ΔＧ°和平衡压力，并导出它们与温度的函数关系。计算指出了同位素分子效应，结果合理。所以，本文所建议的用量子力学方法计算多相化学反应，有应用参考价值。     

计算7Li2振动能级煌振动-转动能级的辛格式矩阵法

利用辛格式矩阵法计算了双原子分子⁷Li₂在A¹Σ_u⁺态的振动能级和振动-转动能级,并与Ley-Koo等的计算结果作了比较.结果显示,辛格式矩阵法是收敛的和可靠的,是计算双原子分子的振动能级和振动-转动能级的合理的数值方法.     

碰撞反应Ca+C2H5Br和Ca+nC3H7Br产物CaBr的内能态分布

采用准经典轨线方法研究了碰撞反应Ca+C2H5Br和Ca+nC3H7Br产物CaBr的内能态分布,计算了产物分子CaBr的平均振动、转动和平动能量以及总可资用能量.结果表明,当碰撞能为7.54kJ/mol时,产物的能量主要为振动能量;随着碰撞能增加,产物的平动能和转动能增加,而振动能略微减小,最可几振动态向较低振动能级移动;反应物分子内能态分布对产物分子的内能态分布影响很小;反应基团越大,产物的振动能占总可资用能量的比例就越高.碰撞反应Ca+C2H5Br和Ca+nC3H7Br均存在两条竞争的反应路径迁移相碰和直接反应路径.前者产生高振动激发态产物CaBr,后者引起C-Br键断裂.当碰撞能增加时,两种反应均倾向于后者.     

NO分子(5σ)~2(1π)~43p-(5σ)~2(1π)~3(2π)~2构形相互作用与转动能级结构

在考虑ＮＯ分子的（５σ）２（１π）４３ｐ－（５σ）２（１π）３（２π）２构形相互作用的情况下，对Ｄ２Σ＋（ｖ＝６），Ｃ２Π（ｖ＝６），Ｂ２Π（ｖ＝２４）和Ｌ２Π（ｖ＝４）电子态的转动能级结构以及态函数进行了计算，计算结果与实验结果很相符。     

用电离光谱技术测量钾分子激发态的振动常数

用染料激光激发钾蒸气，观察到了与钾分子电子态5^3Hu振动能级相关的电离谱，根据电离谱峰对应的激光波长值计算出了钾分子5^3Hu态的振动结构常数，在实验误差范围内与Magnier和Millie的理论计算结果一致。     

NeICl体系振动预解离的含时黄金规则近似处理

在相互作用绘景中运用含时黄金规则波包近似方法，对ＮｅＩＣｌ体系的振动预解离进行计算。这里的波包传播法消除了全量子方法中需要长的传播时间的困难，又由于采用了相互作用绘景，可以选取大的时间传播步长，只需很少的传播步数即可得到解高寿命及终产物的转动态分布。     

Vibrational structure and predissociation rates of the He-O2 vander Waals complex

Using the recently reported full ab initio potential energy surface, the vibrational structure and predissociation dynamics of the He-O₂ van der Waals complex are theoretically investigated. Once the He-O₂ is in a vibrationally excited state, for instance, by infrared radiation, even the one quantum deactivation in vibrational motion releases an energy exceeding the van der Waals bond energy between He and O₂ to break the bond. This vibrational predissociation phenomenon is theoretically investigated using a relative new and simple quantal method. The bound vibrational structure of the He-O₂ complex, the predissociation rates for various vibrational levels, and the rotational distributions of the product O₂, etc. are all predicted. Discussions are focused on the nature of the proposed theoretical method.     

不同初始振动态下D2O在B带的态-态光解动力学

利用高精度的非绝热从头算势能面,采用量子实波包方法研究了D₂O在3个不同初始振动态(0,1,0)、(1,0,0)和(0,0,1)下光激发到~B态解离过程的态-态量子动力学．结果表明,由于初始振动波函数的形状不同,从不同振动态产生的吸收光谱、产物分布和产物分支比具有不同的动力学特性．弯曲振动态(010)的吸收谱呈现出两波瓣的形状且中间具有较浅的极小值,其基态产物OD( ~X)在高能量区域会出现轻微的振动态反转现象．所有初始振动态得到的激发态产物OD(_?)的振-转态分布都随能量的变化出现强烈的震荡,这是由于受到了激发态势能面上长寿命共振态的影响．反对称伸缩振动态(0,0,1)在高能量区域具有较大的产物分支比OD(_?)/OD( ~X),表明绝热通道在某些情形下是主要的解离通道．     

Treatment of the predissociation of the A1Σu+ state of As2 by the interaction with a repulsive state

The rotational analysis of the electronic spectrum of the As₂ molecule has shown a strong predissociation in the A¹Σ_u⁺ state above the v = 7 level. The resultant widths of the rotational absorption lines have been measured for the vibrational levels v = 9 to 15. The numerous experimental data allowed us to consider the predissociation state as a repulsive one according to the C⁺ predissociation case described by Mulliken. A numerical treatment based on a semiclassical method has been performed in order to obtain a good representation of the potential curve of the repulsive state near the crossing point.     

Excitation and relaxation of metastable state NaK(1 3pi) at high vibrational levels

The authors have investigated collision vibrational energy transfer rate constants in NaK[1 3pi(v)] and He system. Pump laser excitation of the spin-forbidden band was used to produce very highly vibrationally excited metastable state NaK[1 3pi (v = 22, 21, 20)]. The probe laser was used to excite the 1 3pi (v = 22, 21, 20) to 5 3pi(v'). Laser induced fluorescence (LIF) from 5 3pi --> 1 3sigma+ transition was used to follow the collision dynamics. The semilog plots of time-resolved LIF was obtained. The slopes yielded the effective lifetimes. From such data several Stern-Volmer plots could be constructed and the relaxation rate constants could be extracted for the sum of all processes that give rise to the decay of the prepared vibrational state. The rate constants (in units of 10(-11) cm3 x s(-1)) for v being 22, 21 and 20 are 1.4 +/- 0.1, 1.2 +/- 0.1 and 1.0 +/- 0.1, respectively. The vibrational relaxation rate is increasing with vibrational quantum number. In order to determine the importance of multiquantum relaxation, it is necessary to measure the relative population of both the prepared state and collisionally populated states. By the kinetic equations governing up to delta(v) = 2 transitions, the time dependence of populations of the vibrational states were obtained. With the help of the integrating the population equations over all time, the importance of the two-quantum relaxation could be studied experimentally. By varying the delay between the pump and the probe laser, the He pressure dependent vibrational state specific decay could be measured. The time evolutions and relative intensities of the three states v = 22, 21 and 20 by preparing v = 22 were obtained. Using experimental data the rate constants (in units of 10(-11) cm3 x s(-1)) for v = 22 --> 21 and v = 22 --> 20 are 0.67 +/- 0.15 and 0.49 +/- 0.12, respectively. The single quantum relaxation accounts for only about 48% of the total relaxation out of v = 22. Multi-quantum relaxation (delta(v) > 1) was found to be important at high vibrational states.     

On the features of statistical behaviour of the O(<Superscript>3</Superscript>P)+HCl(v = 2, j = 1,6,9) → OH + Cl reaction

The O(³P)+HCl(v = 2, j = 1,2,6) → OH+Cl reaction has been theoretically studied by means of a statistical quantum model and an exact time independent method. Although the statistical method is based on the assumption of a complex-forming mechanism, which seems not be the case for this process, the OH(v' = 1) product channel, specially when the HCl reagent is rotationally excited to j = 1, exhibits features of statistical behaviour. In fact, experimental rotational distributions and previous exact quantum mechanical integral cross sections are well described by present statistical results. A possible explanation for this feature is given in terms of the existence of a dynamical well which strongly correlates the initial (v = 2, j = 1) state with the v'=1 final manifold. The method is not capable though to account for the vibrational inversion seen for this process and results obtained for the vibrationless OH formation are in clear disagreement with previous findings.     

原子-振子散射振转激发跃迁几率的理论计算

在相互作用表象中,利用角动量耦合理论,导出了原子-振子散射的含时量子计算公式,并计算了He-H₂体系的振转激发态-态跃迁几率和分散射截面。结果表明:(1)相互作用表象波函数在坐标空间中具有较高的定域性,随时间演化几乎不变形,因此在计算散射量时具有很高的精度,与标准的密耦合(CC)法的计算结果符合很好;(2)增加的振动部分对计算时间的影响取决于对一势能矩阵的积分,而在该积分中仅含基态的计算就能给出较为理想的散射截面,与CC法相比节省近一倍的计算时间。 关键词：     

Theoretical study of nonadiabatic interactions,radiative lifetimes and predissociation lifetimes of excited states of BH

Ab initio multireference configuration interaction calculations have been carried out on the lower-lying electronic states of BH and their nonadiabatic interactions. The ab initio data have been included in subsequent calculations involving solution of the complex eigenvalue Schrödinger equation to determine predissociation widths and lifetimes of vibrational-rotational levels of these states. Secondly, previously calculated ab initio data on the Rydberg states and their nonadiabatic interactions have been included in multi-state vibrational calculations on the 3p and 3d complexes in BH and BD. The results are in good agreement with the experimental analysis of the 3p and 3d spectra in BH and BD. Furthermore, interaction of the 3d states with the neighbouring 4s state is also found to be important.     

Cs(6 ~2D_(5/2))与H_2反应生成的CsH分子的转动和振动态分布

利用激光泵浦-探测技术,在样品池条件下,研究了Cs(6D5/2)态与H2反应生成的CsH分子基电子态的转动和振动的量子态分布。在Cs-H2混合蒸气中,脉冲激光双光子激发Cs(6D5/2)态,另一台调频脉冲激光器扫描CsHX1Σ+(v″,J″)→A1Σ+(v′,J′=J″±1)吸收线,发现CsH分子只有v″=0和1上的振动带上有布居而不布居在v″1的振动带上。v″=0和1上的转动带分布呈现单峰结构,其峰值位于J″=6～8处,转动带分布轮廓与池温下的统计分布接近。转动Boltzmann温度分别为(458±20)K(对v″=1)和(447±18)K(对v″=0),得到的CsH分子的转动温度稍低于池温。从转动态分布得到v″=1与v″=0上布居数之比约为0.897,从而计算出CsH基电子态上的平均转动能ER和平均振动能EV,有效能减去平均振转能得到平均平动能ET。CsH分子3种能量的相对比值fT∶fV∶     

Method of the effective flexible gyroscope in polyatomic molecules

On the basis of the general equations of perturbation theory a procedure is suggested for the partial diagonalization of the vibrational-rotational Hamiltonian of a molecule with respect to the vibrational quantum numbers of a nondegenerate vibrational state. Equations are derived for the complete vibrational-rotational wave function and the “effective” rotational Hamiltonian, which is constructed in such a way that the total energy is represented in the form of a sum of the vibrational and rotational energies.