He+H+2及其同位素取代反应的立体动力学研究

运用准经典轨线方法,基于AQUILANTI势能面, 在碰撞能为145 kJ/mol时,对He+H⁺₂及其同位素取代反应的立体动力学性质进行了理论研究.对k-j′两矢量相关和k-k′-j′三矢量相关的分布函数,以及产物转动取向参数进行了详细的讨论.结果表明,He+HH⁺→HeH⁺+H,He+HD⁺→HeH⁺+ 关键词： 矢量相关 立体动力学 准经典轨线方法     

H2+在阿秒以及双色飞秒激光脉冲中解离时电子位置的相干控制

通过求解含时薛定谔方程, 提出了利用三束激光脉冲控制H₂⁺解离以及解离过程中电子位置的方案. 第一束阿秒激光脉冲将H₂⁺从1sσ_g激发至2pσ_u, 在H₂⁺的解离过程中, 引入两束波长分别为800 nm 与400 nm 的飞秒激光脉冲控制电子在分子内部的运动. 通过改变两束激光脉冲的绝对相位, H₂⁺解离后电子的位置可以得到有效控制(最大有86%的概率使得电子附着在某一个原子核上). 现有的激光技术条件可以在实验上实现这一理论方案. 关键词： 相干控制 电子位置 不对称性参数 2⁺')" href="#">H₂⁺     

两态模型中的振动态布居转移

以氢化锂极性双原子分子为例，运用含时量子波包法数值求解两态模型，从理论方面研究了基电子态X¹Σ⁺通过跃迁偶极矩到激发电子态A¹Σ⁺，两态模型中的振动态布居转移过程.基电子态上以及激发电子态上各自的振动态通过激光脉冲与永久偶极矩作用完成布居转移过程也考虑在内.在紫外光和红外光区域内，使用短的线性偏振激光脉冲实现了高效的布居转移.经过选择激光脉冲的峰值强度、中心频率以及持续时间等参数，在激光脉冲关闭后，最终的布居转移几率都超过了90%.     

HeH+体系光缔合反应的动力学研究

采用含时量子波包方法研究基电子态HeH⁺体系优化的光缔合几率,即He+H⁺→HeH⁺随碰撞粒子对初始动量的变化,并研究伴随该过程的多光子跃迁和解离.选取v=6振动能级为目标态,通过优化激光场参数得到碰撞粒子对的最优光缔合几率.结果表明：随着碰撞粒子对初始动量的增加,光缔合所用的最优激光场的持续时间逐渐减少,但光场的强度和失谐逐渐增加.在某些初始碰撞动量附近,由于共振多光子跃迁过程的存在,最优的光场不能严格地将碰撞粒子对缔合到目标态.此外,研究表明随着初始动量的增加,系统的超阈值解离几率近似线性地增加到一个最大值,直至饱和强度.并且,在碰撞粒子对的初始动量较大时,超阈值解离主导解离过程.     

光缔合过程中多光子振转态选择性跃迁

研究了光缔合过程中OH分子基电子态的振转态选择性跃迁. 计算结果表明通过选择适当的初始碰撞能与光场参数,两碰撞原子可以利用三光子、四光子与九光子跃迁,从连续态跃迁至目标态. 通过选取较低的光场频率,增加跃迁至目标态的光子数来控制分子布居跃迁至较低的振转态. 在光缔合过程中, 部分缔合的分子通过中间态与背景态重新发生解离,解离过程降低了目标态的布居分布.     

利用基频与倍频脉冲控制扩展“ladder”式跃迁

利用含时量子波包动力学方法研究了两束基频与倍频脉冲控制下的扩展"ladder"式跃迁.通过基频与2倍频脉冲控制分子布居从|0,0态跃迁至|5,0与|5,2态;基频与3倍频脉冲控制分子布居从|0,0态跃迁至|5,3?与|6,2态.计算结果表明,利用两束基频与倍频脉冲,通过"ladder"式跃迁,可以得到近100%的布居跃迁概率.两束脉冲间的相对相位角影响分子的布居分布.当脉冲频率比为1:2时,布居以π为周期变化;当脉冲频率比为1:3时,布居以2π为周期变化.     

超冷铷铯极性分子振转光谱的实验研究

利用激光冷却俘获技术在双暗磁光阱中获得高密度的超冷铷原子和铯原子,通过光缔合方法制备超冷铷铯极性分子.采用共振增强双光子电离技术探测基三重态a³∑⁺的铷铯分子,产率约为10⁴/s.通过改变缔合光频率,获得（2）0⁺,（3）0^-,（2）0^-等分子态的高分辨振转光谱,拟合得到相应的转动常数分别为0.00349 cm^-1,0.00649 cm^-1,0.00372 cm^-1.     

两束重合脉冲控制下的振转态布居转移

利用两束频率比为1:3的重合脉冲控制分子振转态布居转移. 计算结果表明, 初始态|0,0>到目标态|3,1>的跃迁概率接近100%. 两束脉冲的相位可以控制跃迁概率. 当φ ₁ =1.68 π 时, 两束脉冲相互增强, 跃迁概率增加. 当φ ₁ =0.64π 时, 两束脉冲相互抵消, 跃迁概率降低. 第二束脉冲的场强对布居转移过程具有较大影响.     

超冷铯分子0g-长程态的振转光谱研究

通过超冷铯原子光缔合制备激发态的超冷铯分子. 利用冷原子荧光频率调制技术获得了超冷铯分子第一激发态6S_1/2+6P_3/2离解限0_g^-长程态高分辨振转光谱, 计算得到0_g^- 长程态振动量子数从0到51的不同振动能级的转动常数, 和Daniel研究小组的理论结果符合得很好. 关键词： 超冷铯分子 光缔合 振转光谱     

High Resolution Crossed Beams Scattering Study of the F+HD→DF+H Reaction

采用高分辨的氢原子里德堡态标识的飞行时间谱技术,对F+HD→DF+H反应进行了交叉分子束研究. 在2.51～5.60 kJ/mol的8个碰撞能下,测得了部分转动态分辨的微分截面. 实验结果显示,反应产物角分布表现出显著的后向散射,随着碰撞能的提高,角分布会逐渐变宽. 确定了产物振动态分支比随碰撞能变化的关系. 结果显示产物DF表现出高度振动态反转布居,其中DF(v′=3)态是布居数最高的产物态,在3.97 kJ/mol以上还探测到产物DF(v′=1)的信号.     

Triatomic wake effect and the determination of the molecular structure of HD2+ from the Coulomb explosion

A new theoretical model of the triatomic molecular wake effect is proposed and applied to molecular ions D+ 3 and HD+ 2 while passing through a solid.The wake effects resulting from the reactions of the two similar ions with thin carbon foil are also investigated by using the Coulomb explosion technique.The experimental results are in good agreement with theoretical estimates and the molecular structure of HD+ 2 is determined by using the model.     

HD+2，H+3和D+3与固体相互作用和三体尾流效应

从分子离子H⁺₃及其氘化同位素分子离子D⁺₃和HD⁺₂与超薄固体膜相互作用发生库仑爆炸为基础,分析讨论了H⁺₃,D⁺₃和HD⁺₂三种分子离子的形成机理,根据产物能谱分布,利用库仑爆炸技术确定了同位素分子离子HD⁺₂的结构形式,给出具体核间距数值.并确定在实验中不存在线状结构的HD⁺₂.提出一种三原子分子离子和固体相互作用中尾流效应的处理方式,通过和实验结果做比较发现这是一种非常理想的处理三体尾流效应的模式,并用之进一步确认了HD⁺₂的结构形状.文章对H⁺₃,D⁺₃和HD⁺₂三种分子离子的实验结果做了对比和讨论. 关键词： +₂')" href="#">微团簇HD⁺₂ +₃和D⁺₃')" href="#">H⁺₃和D⁺₃ 库仑爆炸 三体尾流势 团簇结构     

Enhanced dissociation of H2+ into highly excited states by UV pulses

We theoretically study the dissociation of H₂⁺ by UV laser pulses as a function of the photon energy ω of the pulse. Our results show that pronounced enhancements of the dissociation into highly excited electronic states can be achieved at some critical ω. This is found to be attributed to a consecutively resonant excitation mechanism where the population is first transferred to the first excited state by absorbing one photon and then to higher states by absorbing another one or more photons at the same internuclear distance. This study indicates that the strong coupling between the lowest two states of H₂⁺ can significantly affect the dissociation through higher lying states.     

Accurate theoretical vibration-rotation energies and transition moments for HD+, HT+, and DT+

In this paper we report a theoretical calculation of vibration-rotation transition wavenumbers and transition moments for HD⁺, HT⁺, and DT⁺ for v, N ≤ 5. The results for HD⁺ agree with the experimental results to within 0.015 cm^?1.     

Dissociative excitation of HD+, D2+ , and DT+ by electron impact

In the framework of the Multi-Channel Quantum Defect Theory (MQDT), a theoretical study of the dissociative excitation is presented. Numerical results for the dissociative excitation cross sections of HD ⁺, D ₂⁺, and DT ⁺ with electrons of energy between 2 and 12 eV are reported. The contribution of the vibrational continua of the two lowest electronic states as explicit ionization channels has been considered. Within a quasi-diabatic representation of the molecular electronic states, the Born expansion of second order is done in the K-matrix evaluation.     

IUPAC critical evaluation of the rotational-vibrational spectra of water vapor. Part II: Energy levels and transition wavenumbers for HDO, HDO, and HDO

This is the second of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This article presents energy levels and line positions of the following singly deuterated isotopologues of water: HD¹⁶O, HD¹⁷O, and HD¹⁸O. The MARVEL (measured active rotational-vibrational energy levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0-22 708, 0-1674, and 0-12 105 cm⁻¹ for HD¹⁶O, HD¹⁷O, and HD¹⁸O, respectively. For HD¹⁶O, 54 740 transitions were analyzed from 76 sources, the lines come from spectra recorded both at room temperature and from hot samples. These lines correspond to 36 690 distinct assignments and 8818 energy levels. For HD¹⁷O, only 485 transitions could be analyzed from three sources; the lines correspond to 162 MARVEL energy levels. For HD¹⁸O, 8729 transitions were analyzed from 11 sources and these lines correspond to 1864 energy levels. The energy levels are checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators. This comparison shows that the measured transitions account for about 86% of the anticipated absorbance of HD¹⁶O at 296 K and that the transitions predicted by the MARVEL energy levels account for essentially all the remaining absorbance. The extensive list of MARVEL lines and levels obtained are given in the Supplementary Material of this article, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. In addition, the transition and energy level information for H₂¹⁷O and H₂¹⁸O, given in the first paper of this series [Tennyson, et al. J Quant Spectr Rad Transfer 2009;110:573-96], has been updated.     

Line positions and energy levels of the O substitutions from the HDO/D2O spectra between 5600 and 8800 cm

Absorption spectra of HDO/D₂O mixtures recorded in the 5600-8800 cm⁻¹ region with a total pressure of water from 13 up to 18 hPa and an absorption path length of 600 m have been analyzed in order to obtain new spectroscopic data for HD¹⁸O and D₂¹⁸O. In spite of the low natural ¹⁸O concentration (about 2×10⁻³ with respect to the ¹⁶O one), about 1100 transitions belonging to HD¹⁸O and more than 280 transitions belonging to D₂¹⁸O have been assigned. Most of the D₂¹⁸O transitions belong to the ν₁+ν₂+ν₃ and 2ν₁+ν₃ bands. Sets of energy levels for seven vibrational states of D₂¹⁸O and four states of HD¹⁸O are reported for the first time. The comparison of the experimental data with the calculated values based on Partridge-Schwenke global variational calculations is discussed.     

Charge asymmetry and rovibrational excitations of HD+

Average values of the interparticle distances for rovibrationally excited HD⁺ are calculated using a method where the Born–Oppenheimer (BO) approximation is not assumed. The difference between the proton–electron and deuteron–electron distances is used to describe the charge asymmetry in the system. All-particle one-centre explicitly correlated Gaussian functions are used in the calculations of the HD⁺ rovibrational states. In this work, the non-BO method is extended to calculate the rovibrational states corresponding to the total rotational quantum number of two (N = 2). The algorithms for calculating the Hamiltonian and overlap matrix elements, and the matrix elements of the analytical energy gradient determined with respect to the exponential parameters of the Gaussians, are presented. The gradient is employed in the variational optimisation of the parameters, which is key in obtaining very accurate rovibrational energies in the calculations. The algorithm for calculating the average interparticle distances is also shown. The charge asymmetry of HD⁺ near the dissociation limit occurs, as expected, with the electron preferentially being near to the deuteron. The asymmetry for a particular vibrational level increases with rotational excitations. The rovibrational transition energies are also calculated and compared with available experimental data.