多原子体系非绝热动力学的近似理论方法

非绝热动力学普遍存在于光物理和光化学过程中。描述非绝热跃迁需要处理电子-原子核间的相互耦合运动。由于计算量随体系尺度增大剧烈增长,准确的量子动力学计算目前只适用于描述小分子体系。为了研究多原子分子体系的非绝热过程,近年来发展了一些基于量子-经典动力学近似方法。本文将对典型的这类方法包括经典Ehrenfest方法、面跳跃方法、基于Wigner表示的混合量子-经典方法进行简要的介绍,并讨论如何将量子-经典动力学方法与电子结构从头算手段相结合,模拟非绝热过程。重点阐明各种方法的基本思想和优缺点,并对该领域的发展进行展望。     

环聚炔苯和环聚炔吡啶组成的盘状液晶中的电荷转移

用电子转移的半经典模型在量子化学B3LYP/6-31G(d)水平(对单体)和B3LYP/STO-3G水平(对二聚物)对环聚炔苯和环聚炔吡啶组成的盘状液晶体系的电荷转移性质进行了研究. 盘状液晶体系的电荷转移速率主要依赖于重组能和电荷转移矩阵元, 重组能越小, 电荷转移矩阵元越大, 则电荷转移速率常数越大. 计算结果表明, 这些大环化合物比目前广泛研究和应用的苯并菲衍生物组成的液晶有较小的重组能, 所以有更好的电荷转移性质. 计算结果对有效地设计和合成高效的光导材料和载流子输送材料是有帮助的.     

某些电荷转移反应中线性反应坐标确定的反应途径的非唯一性

在电子转移半经典模型的基础上,对氟代苯并菲组成的盘状液晶体系的电荷转移反应进行了研究,其反应动力学参数在量子化学B3LYP/6-31G(d,p)水平进行计算.研究中发现在反应物和产物的构型确定后,用线性反应坐标构造的反应途径和过渡态的构型不是唯一的.其原因是反应物和产物确定后,其独立内坐标的选择并不是唯一的.因此在计算电荷转移速率常数时必须考虑到多个过渡态构型才能得到定性正确的结果.     

AcCz-2TP分子热活化延迟荧光机制的理论研究

运用半经典的Marcus理论,结合密度泛函理论和含时密度泛函理论的计算方法,研究了AcCz-2TP分子的热活化延迟荧光(TADF)机制.研究结果表明,AcCz-2TP分子的系间窜跃速率和反系间窜跃速率分别为9. 48×106和2. 40×103s-1,能够与其荧光辐射速率(2. 49×104s-1)和磷光辐射速率(0. 32 s-1)互相竞争.目前的计算结果合理地解释了基于AcCz-2TP分子的有机发光二极管器件的外量子效率较低的原因.     

染料敏化太阳能电池界面电荷转移机理

正近日,中国科学院半导体研究所骆军委研究员课题组在Marcus电荷转移理论的基础上使用第一性原理计算方法对染料敏化太阳能电池中的界面电荷转移速率进行了抽丝剥茧式的研究,在比较了TiO_2基和ZnO基染料敏化太阳能电池界面电荷转移过程后,他们发现TiO_2和ZnO等宽禁带半导体作为电荷转移的受主需要密集的带边电子态,这些带边电子态各自提供了电荷转移通道,它们的密集程度对界面电荷转移速率起了决定性     

羟基取代苯并菲化合物分子的结构与电荷传输性质研究

在量子化学B3LYP/6-31G**水平上对苯并菲, 氟及羟基取代苯并菲化合物分子及其分子离子的结构进行理论研究, 得到稳定构型. 在此基础上, 计算二聚物的单点能随旋转角度和盘间距离的变化关系, 得到能量最低点. 根据电子转移的半经典模型计算了苯并菲及氟和羟基取代苯并菲化合物分子的电荷转移常数, 氟和羟基的引入使正电荷转移速率常数明显减小, 即不利于正电荷的传输, 对负电荷的传输速率常数影响不大.     

PBFC-PI量子动力学方法及应用

对多原子体系的量子动力学计算非常重要, 然而, 对含六原子以上的分子体系进行精确量子动力学计算仍具挑战性. 面向过程的基函数定制(PBFC)-并行迭代(PI)方法是一种高效的量子动力学方法, 已应用于对含九原子的丙二醛异构体系的氢迁移速率的精确量子计算. 本综述首先阐明了PBFC的基本思想, 之后重点回顾了PBFC-PI方法的具体内容、 该方法与其它方法的结合及其应用方面的新进展. 应用这些方法实现了对单氢迁移、 协同双氢迁移和分步双氢迁移3种类型基准体系的大规模并行计算, 有助于获得对氢迁移过程的新认识.     

PBFC-PI量子动力学方法及应用（英文）

对多原子体系的量子动力学计算非常重要,然而,对含六原子以上的分子体系进行精确量子动力学计算仍具挑战性.面向过程的基函数定制(PBFC)-并行迭代(PI)方法是一种高效的量子动力学方法,已应用于对含九原子的丙二醛异构体系的氢迁移速率的精确量子计算.本综述首先阐明了PBFC的基本思想,之后重点回顾了PBFC-PI方法的具体内容、该方法与其它方法的结合及其应用方面的新进展.应用这些方法实现了对单氢迁移、协同双氢迁移和分步双氢迁移3种类型基准体系的大规模并行计算,有助于获得对氢迁移过程的新认识.     

含酯基和酰胺基支链的苯并菲液晶电荷传输性质的量子化学研究

根据Marcus半经典模型,计算了支链中含酰胺基和含酯基的苯并菲盘状液晶化合物C18H6(OC2H5)3(OCH2CONHCH3)3和C18H6(OC2H5)3(OCH2COOCH3)3的电荷转移反应的速率常数。这两种化合物的支链都可以对称性分布,也可以非对称性分布。计算表明,支链排列的对称性对电荷转移矩阵元和电荷传输速率常数的影响很大,非对称性分子的正电荷传输速率常数和负电荷传输速率常数均大于对称性分子。所以,取代基非对称性排列对增加电荷传输速率常数有利。其原因是支链非对称排列的分子的质量中心与几何中心不重合,当液晶分子绕质量中心旋转的同时形成了分子间的相对平移,从而增大了电荷转移矩阵元。本文为设计、改善液晶分子的电荷传输性能提供了一条新的思路。     

第一性原理研究由金属镍和钇稳定的氧化锆所形成的三相边界微观结构

基于第一性原理计算并结合经典的蒙特卡罗方法对镍团簇在钇稳定的氧化锆（YSZ）表面的各种稳定吸附构型进行了结构搜索,并得到了不同于以往文献中报道的更稳定的三相边界构型. 在此基础上,对氧迁移时所伴随的电荷转移进行了深入的探讨. 这里,从YSZ到Ni 上的电子转移是描述固体氧化物燃料电池阳极电化学反应的关键,因此,我们进一步分析了影响电荷转移量的可能因素. 所得研究结果暗示着在SOFC阳极可能存在着新的电化学反应机制.     

Theories and Applications of Mixed Quantum-Classical Non-adiabatic Dynamics

Electronically non-adiabatic processes are essential parts of photochemical process, collisions of excited species, electron transfer processes, and quantum information processing. Various non-adiabatic dynamics methods and their numerical implementation have been developed in the last decades. This review summarizes the most significant development of mixed quantum-classical methods and their applications which mainly include the Liouville equation, Ehrenfest mean-field, trajectory surface hopping, and multiple spawning methods. The recently developed quantum trajectory mean-field method that accounts for the decoherence corrections in a parameter-free fashion is discussed in more detail.     

Coherent switching with decay of mixing: an improved treatment of electronic coherence for non-Born-Oppenheimer trajectories

The self-consistent decay-of-mixing (SCDM) semiclassical trajectory method for electronically nonadiabatic dynamics is improved by modifying the switching probability that determines the instantaneous electronic state toward which the system decoheres. This method is called coherent switching with decay of mixing (CSDM), and it differs from the previously presented SCDM method in that the electronic amplitudes controlling the switching of the decoherent state are treated fully coherently in the electronic equations of motion for each complete passage through a strong interaction region. It is tested against accurate quantum mechanical calculations for 12 atom-diatom scattering test cases. Also tested are the SCDM method and the trajectory surface hopping method of Parlant and Gislason that requires coherent passages through each strong interaction region, and which we call the "exact complete passage" trajectory surface hopping (ECP-TSH) method. The results are compared with previously presented results for the fewest switches with time uncertainty and Tully's fewest switches (TFS) surface hopping methods and the semiclassical Ehrenfest method. We find that the CSDM method is the most accurate of the semiclassical trajectory methods tested. Including coherent passages improves the accuracy of the SCDM method (i.e., the CSDM method is more accurate than the SCDM method) but not of the trajectory surface hopping method (i.e., the ECP-TSH method is not more accurate on average than the TFS method).     

Conical intersections and semiclassical trajectories: comparison to accurate quantum dynamics and analyses of the trajectories

Semiclassical trajectory methods are tested for electronically nonadiabatic systems with conical intersections. Five triatomic model systems are presented, and each system features two electronic states that intersect via a seam of conical intersections (CIs). Fully converged, full-dimensional quantum mechanical scattering calculations are carried out for all five systems at energies that allow for electronic de-excitation via the seam of CIs. Several semiclassical trajectory methods are tested against the accurate quantum mechanical results. For four of the five model systems, the diabatic representation is the preferred (most accurate) representation for semiclassical trajectories, as correctly predicted by the Calaveras County criterion. Four surface hopping methods are tested and have overall relative errors of 40%-60%. The semiclassical Ehrenfest method has an overall error of 66%, and the self-consistent decay of mixing (SCDM) and coherent switches with decay of mixing (CSDM) methods are the most accurate methods overall with relative errors of approximately 32%. Furthermore, the CSDM method is less representation dependent than both the SCDM and the surface hopping methods, making it the preferred semiclassical trajectory method. Finally, the behavior of semiclassical trajectories near conical intersections is discussed.     

A multi-scale method for the calculation of charge transfer rates through the Pi-stack of DNA: application to DNA dynamics

We describe an ultra-fast, multi-scale method for calculating charge transfer rates through the pi-stack of DNA using a simple charge hopping model in conjunction with the Marcus equation. The calculation of the parameters required as input to the Marcus equation, such as the electronic coupling and the driving force, are calculated with a combination of quantum mechanical methods and conformations sampled from classical molecular dynamics (MD) simulations. The resulting set of time dependent rate equations are then solved stochastically using Monte Carlo (MC) methods. We have applied this model to investigate the importance of thermal fluctuations in DNA conformation over picosecond and nanosecond timescales, and have identified the timescales of most relevance to hole transfer through DNA.     

Non-Born-Oppenheimer trajectories with self-consistent decay of mixing

A semiclassical trajectory method, called the self-consistent decay of mixing (SCDM) method, is presented for the treatment of electronically nonadiabatic dynamics. The SCDM method is a modification of the semiclassical Ehrenfest (SE) method (also called the semiclassical time-dependent self-consistent-field method) that solves the problem of unphysical mixed final states by including decay-of-mixing terms in the equations for the evolution of the electronic state populations. These terms generate a force, called the decoherent force (or dephasing force), that drives the electronic component of each trajectory toward a pure state. Results for several mixed quantum-classical methods, in particular the SCDM, SE, and natural-decay-of-mixing methods and several trajectory surface hopping methods, are compared to the results of accurate quantum mechanical calculations for 12 cases involving five different fully dimensional triatomic model systems. The SCDM method is found to be the most accurate of the methods tested. The method should be useful for the simulation of photochemical reactions.     

Time-dependent density functional theory Ehrenfest dynamics: collisions between atomic oxygen and graphite clusters

An ab initio direct Ehrenfest dynamics method with time-dependent density functional theory is introduced and applied to collisions of 5 eV oxygen atoms and ions with graphite clusters. Collisions at three different sites are simulated. Kinetic energy transfer from the atomic oxygen to graphite local vibrations is observed and electron-nuclear coupling resulting in electronic excitation within the graphite surface as well as alteration of the atomic charge is first reported in this paper. The three oxygen species studied, O(3P), O-(2P), and O+(4S), deposit different amounts of energy to the surface, with the highest degree of damage to the pi conjugation of the cluster produced by the atomic oxygen cation. Memory of the initial charge state is not lost as the atom approaches, in contrast to the usual assumption.     

Analysis of bridge-mediated pathways for long-range charge transfer systems

With the density matrix decomposition scheme of the path integral method, an accurate quantitative analysis on bridge-mediated pathways in long-range charge transfer processes is presented. Unlike a donor-bridge-acceptor triad, a long-range charge transfer process with a number of bridges has additional pathways in which charges always migrate through bridges but not necessarily by incoherent nearest-neighbor hopping. By employing the density matrix decomposition and sorting the incoherent nearest-neighbor and the coherent next-nearest-neighbor hopping pathways, respective contributions to the charge transfer are evaluated quantitatively. Numerical results of two series of configurations with varying degrees of coherence within the system have found that, depending on the configuration, the contribution of the coherent pathways other than superexchange pathways is significant. In the presence of the coherence, long-range charge transfer dynamics may be dominated by the through-bridge mechanism that consists of the coherent through-bridge pathways as well as the incoherent nearest-neighbor hopping pathways.     

Measuring nonadiabaticity of molecular quantum dynamics with quantum fidelity and with its efficient semiclassical approximation

We propose to measure nonadiabaticity of molecular quantum dynamics rigorously with the quantum fidelity between the Born-Oppenheimer and fully nonadiabatic dynamics. It is shown that this measure of nonadiabaticity applies in situations where other criteria, such as the energy gap criterion or the extent of population transfer, fail. We further propose to estimate this quantum fidelity efficiently with a generalization of the dephasing representation to multiple surfaces. Two variants of the multiple-surface dephasing representation (MSDR) are introduced, in which the nuclei are propagated either with the fewest-switches surface hopping or with the locally mean field dynamics (LMFD). The LMFD can be interpreted as the Ehrenfest dynamics of an ensemble of nuclear trajectories, and has been used previously in the nonadiabatic semiclassical initial value representation. In addition to propagating an ensemble of classical trajectories, the MSDR requires evaluating nonadiabatic couplings and solving the Schro?dinger (or more generally, the quantum Liouville-von Neumann) equation for a single discrete degree of freedom. The MSDR can be also used in the diabatic basis to measure the importance of the diabatic couplings. The method is tested on three model problems introduced by Tully and on a two-surface model of dissociation of NaI.