非平衡体系-热库纠缠定理与热输运（英文）

将最近建立的体系-热库纠缠定理(SBET)扩展到非平衡的情形.其中,任意体系与处于不同温度的多个高斯型热库环境相耦合.现有的SBET将体系-热库的纠缠响应函数与体系的局域响应函数联系起来,而扩展的理论则关注通过分子结的非平衡稳态量子输运流.新理论是基于广义Langevin方程建立的,它与量子情形下的非平衡热力学密切相关.     

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。     

ABEEM方法预测响应函数

在密度泛函理论和原子-键电负性均衡模型基础上,定义了与化学键有关的响应函数以及化学键区域的Fukui函数,建立了一套快速确定分子中各区域(包括原子区域和化学键区域)响应函数的新方法.对大量分子的响应函数的计算结果表明,该方法得到的响应函数可以较好地预测分子中各点的反应活性,并更加快捷省时,展示了原子-键电负性均衡模型的广阔应用前景.     

一个纳入活化络合非平衡效应的TST公式体系

在唯象理论的层次上评述了活化络合体系的非平衡性引起的非平衡统计问题;通过分析活化络合过程的耗散与涨落对反应速度的影响,提出了一个纳入了活化络合过程非平衡效应的TST公式体系代替活化络合平衡常数,建立了活化络合耗散函数与反应速度的关系.同时讨论了影响反应活化络合进程耗散-涨落的诸因素所导致的速度常数统计漂移     

量子耗散与量子输运的级联方程组方法

级联方程已成为研究量子开放系统的稳态性质和动力学过程的重要方法。本文旨在系统综述量子耗散和量子输运的级联方程组方法的建立、发展以及在理论、算法和应用方面的一些最新进展。级联方程形式理论的建立以影响泛函路径积分为基础,并具有数值上的高效性和应用上的灵活性,可用于研究分子体系的复杂动力学过程以及强关联电子体系中的量子输运。其级联耦合结构以非微扰的方式揭示了多体相互作用、体系-环境耦合、非马尔可夫记忆等的综合效应。作为应用示例,我们采用级联方程模拟了生物光富集体系的二维相干动力学光谱以及含时电子输运过程中的动态近藤效应。     

量子相空间中微扰理论

在Torres-Vega和Frederick所提出来的量子相空间理论(简作TF量子相空间理论)的框架下,研究了量子相空间表象下的微扰理论,得出了量子相空间理论框架下的非简并微扰理论(perturbation theory),得到了体系存在微扰情况下的能量和波函数,并且以一维电解质在外加电场中的极化率为例,在量子相空间表象下,对量子体系的状态进行了分析.以期探索出将量子相空间理论和各种近似方法结合起来处理真实体系的问题.     

二氧化碳-水混合体系的相平衡和汽-液-液三相点研究

在微扰链统计缔合流体理论(PC-SAFT)的基础上建立了适用于二氧化碳-水体系相行为研究的状态方程, 以汽-液平衡和液-液平衡实验数据关联体系的交叉作用参数, 关联结果与实验数据吻合良好. 预测了二氧化碳-水体系存在汽-液-液三相平衡的温度和压力区间, 确定了三相点的汽-液-液三相密度及其与温度和压力的关系.     

CdTe量子点-罗丹明6G荧光共振能量转移体系的构建及其应用研究

采用巯基化合物修饰的CdTe量子点构建了量子点(供体)-罗丹明6G(受体)荧光共振能量转移体系, 研究了CdTe量子点与牛血清白蛋白(BSA)的相互作用. 结果表明, CdTe量子点与BSA相互作用后提高了CdTe量子点-罗丹明6G 体系的荧光共振能量转移(FRET)效率, 减小了CdTe量子点和罗丹明6G分子间的距离(r), 证实BSA是通过其色氨酸(Trp)残基与CdTe量子点表面金属发生配位作用而直接结合到量子点表面的.     

基于ZnS量子点荧光淬灭-恢复方法测定还原型谷胱甘肽

水相中合成了3-巯基丙酸保护的非重金属ZnS量子点。根据Ni2+存在的情况下,ZnS量子点荧光强度的恢复程度与谷胱甘肽浓度成正比的现象,建立了基于ZnS量子点荧光淬灭-恢复测定谷胱甘肽的新方法。考察了溶液pH值以及Ni2+浓度对检测体系的影响。在pH 8.5,Ni2+60μmol/L条件下,谷胱甘肽在0～600μmol/L浓度范围内与量子点荧光恢复程度呈良好的线性关系,检出限为3.3μmol/L。本方法可用于实际样品中谷胱甘肽的检测,回收率为94.0%～102.0%。     

混合量子-经典方法计算电荷转移速率及其在实际体系中的应用(英文)

混合量子-经典方法在复杂分子体系动力学过程的模拟方面有重要应用.我们采用Ehrenfest方法、surfacehopping方法和混合量子经典Liouville方程计算了在非绝热极限下的电荷转移速率.然后将这三种方法应用于有机半导体材料电荷转移速率的计算.研究结果发现,Ehrenfest方法和surface hopping方法可能严重偏离正确的结果.偏离的原因是这两种方法没有正确处理相干项的运动,而且这种偏离在涉及到高频模式时显得更加严重.     

Exact quantum master equation via the calculus on path integrals

An exact quantum master equation formalism is constructed for the efficient evaluation of quantum non-Markovian dissipation beyond the weak system-bath interaction regime in the presence of time-dependent external field. A novel truncation scheme is further proposed and compared with other approaches to close the resulting hierarchically coupled equations of motion. The interplay between system-bath interaction strength, non-Markovian property, and required level of hierarchy is also demonstrated with the aid of simple spin-boson systems.     

Accurate Calculation of Equilibrium Reduced Density Matrix for the System-Bath Model: a Multilayer Multiconfiguration Time-Dependent Hartree Approach and its Comparison to a Multi-Electronic-State Path Integral Molecular Dynamics Approach?

An efficient and accurate method for computing the equilibrium reduced density matrix is presented for treating open quantum systems characterized by the system-bath model. The method employs the multilayer multiconfiguration time-dependent Hartree theory for imaginary time propagation and an importance sampling procedure for calculating the quantum mechanical trace. The method is applied to the spin-boson Hamiltonian, which leads to accurate results in agreement with those produced by the multi-electronic-state path integral molecular dynamics method.     

Generalized Gibbs state with modified Redfield solution: exact agreement up to second order

A novel scheme for the steady state solution of the standard Redfield quantum master equation is developed which yields agreement with the exact result for the corresponding reduced density matrix up to second order in the system-bath coupling strength. We achieve this objective by use of an analytic continuation of the off-diagonal matrix elements of the Redfield solution towards its diagonal limit. Notably, our scheme does not require the provision of yet higher order relaxation tensors. Testing this modified method for a heat bath consisting of a collection of harmonic oscillators we assess that the system relaxes towards its correct coupling-dependent, generalized quantum Gibbs state in second order. We numerically compare our formulation for a damped quantum harmonic system with the nonequilibrium Green's function formalism: we find good agreement at low temperatures for coupling strengths that are even larger than expected from the very regime of validity of the second-order Redfield quantum master equation. Yet another advantage of our method is that it markedly reduces the numerical complexity of the problem; thus, allowing to study efficiently large-sized system Hilbert spaces.     

Correlation and response functions with non-Markovian dissipation: a reduced Liouville-space theory

Based on a recently developed quantum dissipation formulation [R. X. Xu and Y. J. Yan, J. Chem. Phys. 116, 9196 (2002)], we present a reduced Liouville-space approach to evaluate the response and correlation functions of dissipative systems. The weak system-bath interaction is treated properly for its effects on the initial state, the evolution, and the correlation between coherent driving and non-Markovian dissipation. Numerical demonstration shows this correlated effect cannot be neglected even in the calculation of linear response quantities that do not explicitly depend on external fields. Highlighted in this paper is also the proper choice of theory among various formulations in the weak system-bath interaction regime.     

Accurate quantum-mechanical rate constants for a linear response Azzouz-Borgis proton transfer model employing the multilayer multiconfiguration time-dependent Hartree approach

The multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method is applied to simulate the quantum dynamics and thermal rate constant of the Azzouz-Borgis model of proton transfer in a polar solvent. To this end, the original atomistic potential is mapped to a system-bath model. Employing the flux correlation function formalism and importance sampling techniques, accurate quantum mechanical rate constants are obtained, which provide a benchmark for evaluating approximate approaches to study the quantum dynamics of condensed-phase chemical reactions. Furthermore, the validity of the mapping procedure is discussed based on the comparison of the classical dynamics of the original atomistic Azzouz-Borgis model and the mapped system-bath model.     

Modeling vibrational dephasing and energy relaxation of intramolecular anharmonic modes for multidimensional infrared spectroscopies

Starting from a system-bath Hamiltonian in a molecular coordinate representation, we examine an applicability of a stochastic multilevel model for vibrational dephasing and energy relaxation in multidimensional infrared spectroscopy. We consider an intramolecular anharmonic mode nonlinearly coupled to a colored noise bath at finite temperature. The system-bath interaction is assumed linear plus square in the system coordinate, but linear in the bath coordinates. The square-linear system-bath interaction leads to dephasing due to the frequency fluctuation of system vibration, while the linear-linear interaction contributes to energy relaxation and a part of dephasing arises from anharmonicity. To clarify the role and origin of vibrational dephasing and energy relaxation in the stochastic model, the system part is then transformed into an energy eigenstate representation without using the rotating wave approximation. Two-dimensional (2D) infrared spectra are then calculated by solving a low-temperature corrected quantum Fokker-Planck (LTC-QFP) equation for a colored noise bath and by the stochastic theory. In motional narrowing regime, the spectra from the stochastic model are quite different from those from the LTC-QFP. In spectral diffusion regime, however, the 2D line shapes from the stochastic model resemble those from the LTC-QFP besides the blueshifts caused by the dissipation from the colored noise bath. The preconditions for validity of the stochastic theory for molecular vibrational motion are also discussed.     

Proton transfer reactions in model condensed-phase environments: Accurate quantum dynamics using the multilayer multiconfiguration time-dependent Hartree approach

The recently proposed multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) approach to evaluating reactive quantum dynamics is applied to two model condensed-phase proton transfer reactions. The models consist of a one-dimensional double-well "system" that is bilinearly coupled to a "bath" of harmonic oscillators parameterized to represent a condensed-phase environment. Numerically exact quantum-mechanical flux correlation functions and thermal rate constants are obtained for a broad range of temperatures and system-bath coupling strengths, thus demonstrating the efficacy of the ML-MCTDH approach. Particular attention is focused on the regime where low temperatures are combined with weak system-bath coupling. Under such conditions it is found that long propagation times are often required and that quantum coherence effects may prevent a rigorous determination of the rate constant.     

Accuracy of second order perturbation theory in the polaron and variational polaron frames

In the study of open quantum systems, the polaron transformation has recently attracted a renewed interest as it offers the possibility to explore the strong system-bath coupling regime. Despite this interest, a clear and unambiguous analysis of the regimes of validity of the polaron transformation is still lacking. Here we provide such a benchmark, comparing second order perturbation theory results in the original untransformed frame, the polaron frame, and the variational extension with numerically exact path integral calculations of the equilibrium reduced density matrix. Equilibrium quantities allow a direct comparison of the three methods without invoking any further approximations as is usually required in deriving master equations. It is found that the second order results in the original frame are accurate for weak system-bath coupling; the results deteriorate when the bath cut-off frequency decreases. The full polaron results are accurate for the entire range of coupling for a fast bath but only in the strong coupling regime for a slow bath. The variational method is capable of interpolating between these two methods and is valid over a much broader range of parameters.