处理NaCs光解离问题的两种方案比较

利用含时波包动力学方法中的劈裂算符-傅里叶变换传播方案和切比雪夫多项式展开方案研究了NaCs分子的光吸收截面，并对由这两种方案计算得出的结果进行了比较.结果表明劈裂算符-傅立叶变换传播方案能更好地展示光吸收截面的中间动力学信息，而在研究初始波包与光吸收截面的关系时，由切比雪夫多项式展开方案获得的结果则更直观.利用后一方案计算的从基态 不同振动态跃迁到激发态 上相应的光吸收截面的结果表明，初始波包对光吸收截面有一定的影响，所有振动态的吸收截面均表现出谐振行为，即每一个振动态吸收截面最小值的个数恰好等于基态振动态波函数节点的个数，这种节点映射行为与映射原理相符合.     

含时波包法研究NaH分子的光解截面

采用傅立叶格点哈密顿方法求解含时薛定谔方程、劈裂算符方法传播波函数,计算了NaH分子在三组势能曲线下从初始态X1Σ (v″=0)跃迁到激发态B1Π的光解截面.研究表明影响光解截面最大值及相应光子能量的关键因素是解离阈能,势能曲线间相对小的平移对计算结果影响不大.应用含时量子力学方法计算光解截面时,车比雪夫多项式方案和劈裂算符方法能够给出基本相同的结果.     

一维谐振子量子运动中的经典特性

利用量子力学的态叠加原理和算符劈裂法,对处于一维谐振子势中的初始态为高斯波包的中心位置的量子运动进行了研究.结果表明:其中心位置的量子运动呈现出经典谐振子的运动特性;波包的初始位置和初始时刻所加动量对波包中心位置量子动力学的影响与经典谐振子类似条件对运动的影响有相同的性质.本结果对理解复杂量子运动中的高斯波方法有一定的启示作用.     

含时波包动力学方法研究飞秒激光场下NH3分子通过中间预解离态(A)的光电子能谱

本文首次利用二维含时波包动力学理论研究了飞秒激光场下NH3分子通过中间预解离态(A)的共振增强多光子电离光电子能谱(REMPI-PES),得到了与实验相同的结果.计算中应用多项式函数拟合从头算结果得到的内坐标下的二维解析势能面包括基态(X)、中间预解离态(A)以及其它准连续的电子-离子对态,并经坐标变换得到质量加权坐标系下的相应势能面.劈裂算符-快速傅立叶变换(FFT)方法是波包传播的基本方法.计算分析表明,脉冲的形状(强度、脉宽等)对光电子能谱有着很大的影响,能谱中的三组峰簇可以认为是由强场对势能面的影响引起的,因而强场效应是解释飞秒时间分辨光电子能谱的关键.这种思想对实现原子和分子过程的相干控制具有重要的意义.     

含时波包动力学方法研究飞秒激光场下NH3分子通过中间预解离态A^～的光电子能谱

本首次利用二维含时波包动力学理论研究了飞秒激光场下NH3分子通过中间预解离态A^～的共振增强多光子电离光电子能谱(REMPI—PES)，得到了与实验相同的结果。计算中应用多项式函数拟合从头算结果得到的内坐标下的二维解析势能面包括基态X^-、中间预解离态A^～以及其它准连续的电子-离子对态，并经坐标变换得到质量加权坐标系下的相应势能面。劈裂算符-快速傅立叶变换(FFT)方法是波包传播的基本方法。计算分析表明，脉冲的形状(强度、脉宽等)对光电子能谱有着很大的影响，能谱中的三组峰簇可以认为是由强场对势能面的影响引起的，因而强场效应是解释飞秒时间分辨光电子能谱的关键。这种思想对实现原子和分子过程的相干控制具有重要的意义。     

利用强飞秒激光脉冲串传递相干波包

用一维两态波包动力学模型从理论上研究了碘分子在两个激光脉冲串作用下有泵浦－拉下过程。计算中碘分子的基态和激发态势能面采用莫尔斯势能面,含时薛定谔方程通过分裂算符快速富里叶变换方法求解,基电子态的振动本征函数采采不连续变量方法计算,初步波包选择为电子基态的振动基本征函数,两个势能面之间的耦合采用偶极近似,激光脉冲的形状选择为高斯脉冲。利用上述的含时波包法实时地模拟了碘分子通过中间Ｂ态向基电子Ｘ态的高     

O~++H_2→OH~++H反应的动力学研究

采用含时量子波包方法结合二阶分裂算符传播子对初始态为(v=0, j=0)的O~++H_2→OH~++H反应体系在0.01—1.00 eV的碰撞能范围内进行了态分辨理论水平上的动力学计算.对反应概率、积分截面、微分截面以及固定初始态的热速率常数等动力学信息进行了计算并与文献报道的实验和理论结果进行了比较.结果表明本文的理论结果与实验结果十分符合.从微分截面的散射信息可知,在低碰撞能范围内,插入反应机制在反应中占据主导地位.随着碰撞能的增加,反应机制逐渐由插入机制变为抽取反应机制.     

啁啾脉冲对氢分子离子解离动力学的影响北大核心CSCD

本文通过数值求解一维含时薛定谔方程,理论研究了超短啁啾脉冲(5fs,790nm)对处于低振动态氢分子离子解离动力学的影响.研究过程中有效利用流算符的方法得到不同激光强度下的解离几率及核波包密度分布.结果表明:低强度的啁啾脉冲可显著增强低振动态氢分子离子的解离过程,使解离过程提前发生并在较短的时间内获得较多的解离产物,并给出相应的理论解释.     

啁啾脉冲对氢分子离子解离动力学的影响

本文通过数值求解一维含时薛定谔方程,理论研究了超短啁啾脉冲（5-fs,790-nm）对处于低振动态氢分子离子解离动力学的影响. 研究过程中有效利用流算符的方法得到不同激光强度下的解离几率及核波包密度分布. 结果表明：低强度的啁啾脉冲可显著增强低振动态氢分子离子的解离过程,使解离过程提前发生并在较短的时间内获得较多的解离产物, 并给出相应的理论解释.     

Airy波包及其自加速效应(续1)

正3艾里波包根据相对速度的伽利略变换,研究含时薛定谔方程的解——可积分的波包在自由空间的动力学行为,求解出自由空间艾里波包的运动规律和量子力学中艾里波包的唯一性.3.1薛定谔方程的解——艾里波包在伽利略推导的复合速度移动变换框架下,贝里-巴拉兹含时薛定谔方程的艾里函数解是可积分的波包,这个波包有一定的势能和能量,随着时间增加到零,然后再传播.贝里-巴拉兹表示出了一个极限形式的自由粒子的波包.     

Theoretical simulation of the photoassociation process for NaCs

We investigate the two-step association process of NaCs using the time-dependent wave packet method.Ground state atoms can be photoassociated to the low vibrational levels of the ground state for an NaCs molecule by the two-step association.The time-dependent Schro¨dinger equation of the association process is solved within a three-state model and the wave packet is propagated with the "split operator-Fourier transform" scheme and the rotating-wave approximation(RWA).The vibrational population distribution of the ground state can be obtained by projecting the wave packet to every vibrational level of the ground state.The results not only show that for NaCs achievement of photoassociation production is accompanied by the photodissociation of the higher vibrational molecules,but also show that the vibrational distribution in lower vibrational levels of the ground state changes with the laser parameters.     

Temperature dependence of an electron attachment to chlorine molecules

The cross section of electron attachment to chlorine molecules was calculated with the Condon reflection method for various populations of vibrational levels of the ground molecule state. The populations are defined by a prescribed vibrational temperature. The vibrational wave functions were obtained by numerically solving the Schrödinger equation, and required parameters of the potentials of upper ion states were taken, so as to minimize the deviation between calculated and room-temperature experimental data on the cross section of electron attachment.     

Time-dependent approach to the double-channel dissociation of the NaCs molecule induced by pulsed lasers

The dynamics of the double-channel dissociation of the NaCs molecule is investigated by using the time-dependent wave packet （TDWP） method with the ＂split operator-Fourier transform＂ scheme. At a given wavelength and intensity of laser pulse, the population of each state changing with time is obtained. The photo-absorption spectra and kinetic- energy distribution of the dissociation fragments, which exhibit vibration-level structure and dispersion of the wave packet, respectively, are also obtained. The results show that by increasing the laser intensity, one can find not only the band center shift of the photo-absorption spectrum, but also the change of the fragment energy. The appearance of the diffusive band in the photo-absorption spectrum and the multiple peaks in the kinetic-energy spectrum can be attributed to the effects of the predissoeiation limit and the external field.     

Control of de-excitation to selected vibrational levels in the ground state of NaH molecule using two broadband ultrashort pulses

We show that the de-excitation to different vibrational levels of the ground state in NaH molecule can be controlled by using two delayed ultrashort pulses (4 fs Gaussian). A vibrational wave packet generated on the excited A¹Σ⁺ state by the first pulse is de-excited back to the ground state by a second pulse after a time delay. The cross-section for de-excitation of the wave packet to different vibrational levels of the ground electronic state can be controlled by controlling the delay time between the two pulses as well as by choosing a pulse duration much shorter than the vibrational period of the molecule, such that the de-excited wave packet remains localized in the Franck–Condon region of a particular vibrational level of the ground state. Hence, the de-excitation to a particular vibrational level can be enhanced by suppressing that in others. In spite of the large bandwidth of the pulse which includes nine vibrational levels of the upper state and five vibrational levels of the ground state, one can selectively de-excite the molecule to any one or two vibrational levels of the ground state by carefully choosing the delay time between the pulses and the pulse duration. We are designing the wave packet in the ground state by two short pulses and selectively distributing the population in one or two levels at various values of the delay time. In light molecules having small vibrational period, this selectivity in de-excitation to one or two vibrational levels in the ground state can be achieved only by using ultrashort (4 fs) pulses in the presence of which the localization of the wave packet in the Franck–Condon region of the vibrational levels are particularly possible. It has been shown that the de-excitation cross-section to a particular vibrational level oscillates with delay between the pulses which can be realized as a time-dependent quantum gate.     

Photoassociation of NaRb with an asymmetric laser pulse

We investigate the photoassociation dynamics of cold NaRb molecule controlled by an asymmetric laser pulse called slowly-turned-on and rapidly-turned-off (STRT) laser pulse. This new shaped laser pulse has a remarkable merit, compared with the typical Gauss-type pulses, so that we can efficiently associate molecules with the state expected instead of going back to the continuum state. Using the three-state model, we solve the quantum mechanical equation with the “split operator-Fourier transform” method under the rotating-wave approximation (RWA) in propagation of the wave packet. By the projection of the obtained wave function onto each vibrational state, we can get the vibrational population of the ground electronic state. The results reveal that, with the STRT laser pulse, an efficient photoassociation process can be achieved and the vibrational distribution in the ground state can be controlled by the laser parameters.     

Manifestation of external field effect in time-resolved photo-dissociation dynamics of LiF

The photo-dissociation dynamics of LiF is investigated with newly constructed accurate ab initio potential energy curves (PECs) using the time-dependent quantum wave packet method. The oscillations and decay of the wave packet on the adiabats as a function of time are given, which can be compared with the femtosecond transition-state (FTS) spectroscopy. The photo-absorption spectra and the kinetic-energy distribution of the dissociation fragments, which can exhibit the vibration-level structure and the dispersion of the wave packet, respectively, are also obtained. The investigation shows a blue shift of the band center for the photo-absorption spectrum and multiple peaks in the kinetic-energy spectrum with increasing laser intensity, which can be attributed to external field effects. By analyzing the oscillations of the wave packet evolving on the upper adiabat, an approximate inversion scheme is devised to roughly deduce its shape.     

Optical control of the quantum-state distribution of vibrational wave packets using trains of phase-locked pulses

An intuitive scheme for controlling the quantum state composition of one-coordinate molecular wave packets is developed. The accumulated phase difference between the various components of the molecular wave packet is determined, and then a sequence of phase-locked optical pulses is employed to selectively enhance or depopulate specific vibrational states, or sets of vibrational states. The quantum state composition of the resulting wave packet, and the efficiency of the control scheme, is determined by calculating the multi-pulse response of the time-dependent vibrational state populations.     

Channel mixing effects in the dissociative recombination of H+3 with slow electrons

We discuss the low-energy dissociative recombination of H+3, which strongly influences the abundance of this ion in diffuse interstellar molecular clouds. The kinetic couplings between the ionization continuum and the dissociative ground state of H3 have been used as input to a two-dimensional wave packet calculation of dissociation dynamics. The cross section obtained for direct dissociative recombination is much smaller than the latest experimental results. However, a multichannel quantum defect treatment shows that an indirect mechanism via bound Rydberg states of H3 prevails for this process.