基于能量的轨线面跳跃新退相干修正方法

本文受轨线分叉修正面跳跃(BCSH)方法[J. Xu and L. Wang, J. Chem. Phys. 150，164101 (2019)]的启发，提出了两种轨线面跳跃新退相干时间计算公式. 本研究的线型和指数型公式均将退相干时间刻画为绝热势能面之间能差的函数，能够准确地描述BCSH预测的由波包反射导致的退相干效应. 在包含了200个多样化的系列模型中，采用不同的初始核动量，以精确全量子解为参考，对涉及的参数进行了系统训练. 相比广泛使用的退相干公式，两种新方法在Tully的三个标准模型中都显著地提高了可靠性，并保持高计算效率.     

利用多光子跃迁控制基态HF分子布居转移

采用波包动力学方法研究了HF分子基电子态的多光子跃迁. 激光场由两束频率比为1:2的重合红外脉冲构成. 态|0,0>作为初始态, 态|4,0>与态|4,2>分别作为目标态. 计算结果表明, 通过选取不同的共振频率, 可以控制布居跃迁至不同的目标态. 两束脉冲间的初相位差可以控制布居转移概率. 当初相位差为π/2的偶数倍时, 布居转移概率为最大值. 当初相位差为π/2的奇数倍时, 布居转移概率为最小值. 初相位差对于态|4,0>的布居影响大于态|4,2>. 关键词： 多光子跃迁 初相位 布居转移 波包     

基于绝热快速通道控制原子布居数及其相干性的研究

本文在理论上研究了纳秒数量级内，运用绝热快速通道（ARP）来控制基态原子的相干性及 其布居数在不同能态间的转移.理论计算结果表明抽运激光脉冲相对斯托克斯（Stokes）脉 冲延迟时间的微小改变会导致原子相干性及其布居数的显著变化.运用密度矩阵方程和麦克 斯韦方程联合的自洽方程数值解，我们找到了实现原子最大相干性及其布居数在不同能态间 完全转移的条件. 关键词： 绝热快速通道 布居数 原子相干     

准Λ型四能级中用非匹配高斯脉冲实现相干布居转移

文章研究用非匹配高斯脉冲实现四能级准Λ型系统中的相干布居转移.从密度矩阵方程出发,对四个态的布居数随时间的演化进行了数值模拟.模拟结果表明,泵浦光场的拉比频率强度和失谐量对布居转移率的影响和探测光场、耦合光场的拉比频率强度及失谐量对布居转移率的影响不同;自发辐射诱导相干(SGC)对布居转移率的影响不大.但当它们选取适当参数的时候,基态的布居几乎可以全部被转移到目标态能级.     

激光场强度对NO电子态粒子数布居影响的理论研究

用含时波包方法研究了激光场强度对NO各电子态上粒子数布居的影响.在计算中,采用了四态模型.利用分裂算符傅里叶变换方法求解Schrdinger方程,得到各个电子态的波函数,从而求得各个电子态上粒子数的布居.计算结果表明,不同强度的抽运光对各个电子态上粒子数布居会产生不同的影响.通过改变激光强度可以实现对电离产率的控制,这种思想对实现原子分子过程的激光操控具有重要意义.     

H+MgH+→Mg++H2反应中由非绝热耦合引起的复合物形成反应机理

一个化学反应的过程可能涉及多个绝热电子态,其中的非绝热耦合对反应机理起着重要的作用. 本文采用含时量子波包方法和轨线面跳跃方法研究了非绝热耦合对H+MgH⁺→Mg⁺+H₂反应的影响. 通过理论计算得到了绝热和非绝热近似下的反应态-态分辨的积分截面. 计算结果表明,当计算中忽略非绝热耦合时,反应遵循直接剥离的反应机理. 然而,当计算中包含非绝热耦合时,在反应过程中可以形成一个长寿命的激发态复合物(MgH₂⁺)^*,进而使反应遵循复合物形成反应机理. 通过轨线面跳跃计算,进一步揭示了直接剥离和复合物形成反应机理. 由非绝热耦合引起的复合物形成反应机理不仅提高了反应的活性,并且对产物的振动态分布具有显著影响.     

利用布居囚禁态实现高效率布居转移

利用缀饰原子方法研究了激光同位素分离涉及的一个四能级系统的布居转移过程，发现了类似于三能级系统的布居囚禁态，在此基础上分析了光泵浦过程的布居囚禁现象，提出一种能够利用基态布居及亚稳态热布居的高效率光泵浦方法并以分离轴原子为例说明该方法的优越性。     

基于方波脉冲外场的超冷原子-分子绝热转化

基于受激拉曼绝热通道技术,研究了方波脉冲外场下的超冷原子-双原子分子转化.运用绝热保真度的方法,详细分析了该原子-分子转化系统相干布居俘获态的动力学演化过程.研究发现,相干布居俘获态的最终绝热保真度随脉冲激光强度的变化呈现出大幅度的周期振荡.这表明本文所设计的方波脉冲方案与高斯脉冲方案相比具有明显的优势,可以在较小的脉冲激光强度下达到较高的绝热保真度并实现较高效率的超冷原子-分子转化.     

New ab initio Potential Energy Surfaces for Cl(2P3/2, 2P1/2)+H2 Reaction

采用多参考组态相互作用的计算方法和很大的基组构造了Cl+H₂反应体系的一组新的三维从头算势能面. 该势能面包含Cl+H₂体系的能量最低的三个绝热态,并在非绝热近似下转化为四个非绝热势能面. 另外,旋轨耦合矩阵元也基于Breit-Pauli Hamil-tonian计算得到. 对角化这四个非绝热势能和两个旋轨耦合矩阵元组成的全耦合Hamiltonian,得到了三个考虑旋轨耦合后的绝热势能面.基于这组新势能面的非绝热动力学计算结果与最新的实验符合得很好,很好地解释了     

强磁场中碱金属原子的演化和Aharonov－Anandan相因子

利用量子不变量理论研究了任意随时间变化的强磁场中碱金属原子系统的演化问题，得到了此系统精确的演化态，并利用此精确的演化态求出了相应的Ａｎａｒｏｎｏｖ－Ａｎａｎｄａｎ相因子和绝热极限下的Ｂｅｒｒｙ相因子。将此系统精确的演化态按哈密顿量的瞬时本征态展开，可以得到绝热近似的任意阶修正。     

Constrained relativistic mean-field approach with fixed configurations

A diabatic (configuration-fixed) constrained approach to calculate the potential energy surface (PES) of the nucleus is developed in the relativistic mean-field model. As an example, the potential energy surfaces of ²⁰⁸Pb obtained from both adiabatic and diabatic constrained approaches are investigated and compared. It is shown that the diabatic constrained approach enables one to decompose the segmented PES obtained in usual adiabatic approaches into separate parts uniquely characterized by different configurations, to follow the evolution of single-particle orbits till the very deformed region, and to obtain several well-defined deformed excited states which can hardly be expected from the adiabatic PESs.     

双Λ型原子系统中制备相干叠加态的研究(英文)

本文讨论了在双Λ型原子系统中制备相干叠加态的方法:一个Λ型系统通过控制激光而另一个Λ型系统采用部分受激拉曼绝热通道的方法.在理论上分析了产生任意相干叠加态的可能性并且讨论了透热系统在产生相干叠加态过程中的重要性.研究表明,没有透热过程是不可能制备出任意的叠加态.应用数值方法验证理论分析是正确,并且指出任意叠加态的产生只与控制脉冲的时间延迟有关.     

多粒子W态的绝热制备

通过利用时间依赖的外磁场,提出了绝热制备多粒子W态的新方法.同时给出了驱动n个自旋1/2粒子从未纠缠态到W态的相互作用哈密顿量以及绝热和非绝热演化条件,展示了能量和靶态布据随时间的演化图.     

用Sin-DVR方法求解在绝热表象下锥形交叉分子振动本征态

在波恩-奥本海默近似中,分子中原子核的运动通常采用绝热表象的基态势能面来描述,一般情况下这样是比较好的近似. 然而当势能面上存在锥形交叉时,即使体系的能量远远低于锥形交叉点,绝热基态势能面近似将不再有效. 锥形交叉的出现,使得绝热表象下描述核运动的哈密顿中出现了两个额外的附加项：对角波恩－奥本海默近似校正(DBOC)项和几何相位(GP)项. 尤其GP项,使得基态绝热势能面近似失效. 这两项在锥形交叉点处的数值是发散的,因此在绝热表象中来严格描述核运动,会使量子动力学的计算存在数值收敛的困难. 在量子分子动力学计算中,最常用的数值方法是分离变量表象方法(DVR). 本文通过在绝热表象和透热表象下求解涉及两个电子态且包含锥形交叉的二维的薛定谔方程来验证Sinc-DVR的数值收敛性. 计算结果显示,在绝热表象中采用通常格点密度分布的Sinc-DVR方法,即使在没有特别的处理DBOC和GP项时,也可以得到比较可靠的结果. 此时的数值不确定性并没有比引入任意的向量势来纠正GP效应的不确定性更差. 需要特别注意的是,纠正GP效应的任意向量势的精确形式,通常是不易得到其精确形式的.     

Optical potential discrete variable representation method in the adiabatic representation

The optical potential discrete variable representation method (OP-DVR) has been applied recently to calculate resonances in the framework of the diabatic representation [J. Chem. Phys. 101, 7580 (1994)]. This method is based on the conjoint use of the discrete variable representation (DVR) method and the properties of a complex absorbing potential (CAP). The OP-DVR method is the DVR version of the CAP stabilization method initially proposed by Jolicard and Austin [Chem. Phys. Lett. 121, 106 (1985)]. In the present study, we show that this efficient and accurate method can also be applied within the adiabatic representation since it allows one to overcome in a simple way, numerical difficulties associated with the first derivative operator which appears in the expression of non adiabatic couplings. Within the OP-DVR method, the choice of the representation (diabatic or adiabatic) is governed by physical arguments and by the fact that the potentials and the couplings are known in one or the other of these two representations. In the case where the potentials and the couplings are obtained in the adiabatic representation, we show in this paper that the transformation into the diabatic framework is not necessary. We demonstrate that the discrete variable representation can be a simple and an efficient way to deal with the adiabatic representation. Received: 30 April 1998 / Revised: 29 September 1998 /Accepted: 21 October 1998     

Realization of adiabatic and diabatic CZ gates in superconducting qubits coupled with a tunable coupler

High fidelity two-qubit gates are fundamental for scaling up the superconducting qubit number.We use two qubits coupled via a frequency-tunable coupler which can adjust the coupling strength,and demonstrate the CZ gate using two different schemes,adiabatic and diabatic methods.The Clifford based randomized benchmarking(RB) method is used to assess and optimize the CZ gate fidelity.The fidelities of adiabatic and diabatic CZ gates are 99.53(8)% and 98.72(2)%,respectively.We also analyze the errors induced by the decoherence.Comparing to 30 ns duration time of adiabatic CZ gate,the duration time of diabatic CZ gate is 19 ns,revealing lower incoherence error rate r'_(incoherent,int)=0.0197(5) compared to r_(incoherent,int)=0.0223(3).     

Diabatic interaction potential for nucleus-nucleus collisions

Within a refined method for the construction of diabatic states allowing for the treatment of the full spin-orbit coupling, characteristic features of the diabatic potential for nucleus-nucleus collisions are investigated. Approximately 90% of the strong repulsion results from diabatic particle-hole excitations, while only 10% is due to compression. The diabatic interaction potential describes a physical situation intermediate between adiabatic and sudden approximations.     

Quasi diabatic CASSCF state functions

A new method to determine quasi diabatic (QD) CASSCF states is presented. The adiabatic states are subjected to a unitary transformation resulting from diagonalization of a state-selection operator. The latter is constructed from the overlap of the adiabatic states with a suitable set of reference states. The multi-state (MS) CASPT2 method is used to account for the dynamical correlation effects in an approach where the QD-CASSCF wave functions are used as reference states. The procedure is applied to avoided crossings in excited states of BeH, LiO and ozone. The advantages of the proposed formulation are discussed.     

Theoretical Investigation of Femtosecond-Resolved Photoelectron Spectrum of NaI Molecules

The time-resolved photoelectron spectra （TRPES） of NaI molecules are calculated by using the time-dependent wave packet method. Two different potential energy curves （adiabatic and diabatic） are adopted in the simulation. The third peak of the photoelectron spectra presented in the adiabatic calculation is induced by the reflection of the wave packet. The oscillating of the wave packet onto the diabatic energy curve is a decreasing process. The comparison of the photoelectron spectra between the two different calculations （adiabatic and diabatic） is presented.