虚时间分裂算符方法研究溶剂电子转移动力学

在Sumi-Marcus理论中，采用虚时间分裂算符方法研究电子转移动力学．此方法具体应用于计算嗪-1和N,N-二甲基苯胺分子之间的电子转移速率常数．通过计算得到的两种反应物态的平均速率常数和一个长时间的速率常数，揭示了不同的sink函数时的电子转移动力学．在数值模拟过程中还发现了一些新的电子转移特性．     

光诱导呫吨酮电子转移和氢转移反应的激光闪光光解研究

用时间分辨激光闪光光解的方法研究了在乙腈溶剂中呫吨酮的激发三重态的性质，并得到了呫吨酮激发三重态和胺类、醇类以及酚类反应的瞬态吸收光谱和猝灭速率常数(kq)．除了苯胺和3-硝基苯胺被认为是能量转移外，呫吨酮和其余胺类的反应随着自由能变的减校lgkq逐渐增大，由此认为发生了电子转移反应．而对于二甲基-对甲苯胺、3,5,N,N-四甲基苯胺、N,N-二甲基苯胺、三乙胺来说，通过瞬态吸收光谱的变化可以知道既有电子转移反应又有氢转移反应发生．呫吨酮和醇类只发生氢转移反应，其猝灭速率常数和醇的?-C?H的键能有关．由     

二能级系统的马尔可夫与非马尔可夫方法比较

分别用马尔可夫与非马尔可夫方法推导出二能级系统与库相互作用的耗散动力学,并把失谐谱密度与一个光子带隙的谱密度下的计算结果与精确解进行比较。对于失谐谱密度,分别讨论在马尔可夫与非马尔可夫库的激发态布居数,发现无论是短时的弱耦合区域,还是长时间的强耦合区域,非马尔可夫方法比马尔可夫方法更加接近精确解,而马尔可夫近似主要适用于弱耦合条件;对于光子带隙谱密度,主要考虑了小带宽的布居数,结果显示马尔可夫方法主要适用于弱耦合条件,而非马尔可夫方法主要适用于强耦合情形。结果表明:对于不同谱密度、不同的耦合区域,只有选择合适的马尔可夫或非马尔可夫方法才能精确描述系统的动力学。     

V^2＋（aq）／V^3＋（aq）荷移动力学参数的理论研究

基于电子转移过程与离子水化过程中的基本共同特征，提出了一种确定电子转移过程动力学参数的精确水化函数方案，利用实验振动光谱数据及水合热力学数据，建立了两种用于描述反应体系与中心离子－内氛水分子分离和溶剂重组之间能量关系的精确水化函数。在提出新的活化模型基础上，结合水化函数给出了活化能的计算方案。利用原始Ｌａｎｄａｕ－Ｚｅｎｅｒ理论计算了电子发射系数。所涉及到的位能面的斜率及耦合矩阵元，采用水化函数、     

电子关联动力学

应用高分辨快电子能量损失谱仪，绝对测量了He原子各种光学允许和光学禁戒的双电子激发过程的动量转移依赖特性，报道了作为动量转移函数的以内禀关联量子数K，r和A表征的电子态：(0，1)：‘P0，：(1，0)；s。和：(1，0)；’D。的FarIo参数q以，p。／和．s，同时对：(一1，0)；‘s。和：(1，0)：的波函数作出定性检验．从而在实验上通过激发动力学过程研究了电子关联效应．     

激光闪光光解研究二羟基蒽醌和腺嘌呤/胞嘧啶的电子转移反应

采用纳秒时间分辨的激光闪光光解技术研究了乙腈/水混合溶液中二羟基蒽醌和腺嘌呤或胞嘧啶之间的电子转移反应. 在355 nm紫外光作用下,经由系间窜跃产生的三重态二羟基蒽醌与两碱基分别发生电子转移反应,其中碱基作为典型的电子给体. 基于测量到的反应瞬态中间体的动力学淬灭速率,两个反应过程被认为分步进行,先电子转移之后发生质子转移反应. 通过研究表观淬灭速率与两个碱基浓度的依赖关系,分别得到了两个双分子间电子转移反应的速率常数,分别是9.0×10⁸ L/(mol·s) (胞嘧啶)、3.3×10⁸ L/(mol·s) (腺嘌呤).     

TrpH—TryOH肽链中电子的逆向转移

本文较详细的研究了色氨酰酪氨酸二肽（ＴｒｐＨ－ＴｙｒＯＨ）中的电子转移，电子该电子转移的速率，甚至电子转移的方向都强烈的依赖于溶液的ｐＨ。而且，该肽中的酪氨酸残基瞬态粒子浓度与色氨酸残基瞬态粒子浓度之比也强烈的依赖于ｐＨ。根据这种依赖性，求得了二肽中的ｐＫａ（ＴｒｐＨ＾＋）和ｐＫａ（ＴｙｒＯＨ），其值分别为６．２和１１．３。     

黄素体系电子转移过程光谱研究

黄素类物质在生物体内广泛存在,是许多电子转移反应的活性中心,也是电子传递链的重要组成部分。其受到光照激发后引起的电子转移,是许多生命过程的基础与起始步骤。特别地,一种名为隐花色素的黄素蛋白在光激发后经一系列电子转移形成自旋相关自由基对,被认为是最有可能的生物磁敏物质,更使黄素体系电子转移过程的动力学,特别是自旋动力学过程倍受关注。对黄素电子转移过程及相关机理进行研究,有助于厘清多种生命过程的化学机理与影响因素。为此,科学界综合运用了多种仪器与测试手段,其中主要包括紫外-可见光谱,荧光光谱,瞬态吸收光谱,光化学诱导动态核极化（Photo-CIDNP）技术等。通过多年的研究,对黄素在生物体内的作用机理与电子转移过程的认识经历了由浅入深,不断深入的过程。紫外-可见光谱（UV-Vis）主要用于研究黄素系统中的电子激发,自旋动力学和电子转移。结合理论计算,UV-Vis还可以识别电子转移中涉及的基团并进行定量分析。荧光光谱可以识别电子受激发的物质,在反应过程中观察黄素和半醌中间体的产生和消耗,并确定其氧化还原和质子化状态。瞬态吸收光谱适于观测反应过程中出现的短寿命物种,其中飞秒泵浦探测技术的引入大大提高了观测的时间分辨率,并且可以通过光谱特征区分单重态和三重态的自由基对。光化学诱导动态核极化核磁共振（NMR）可以直接观察电子-核自旋动力学过程。磁场依赖性photo-CIDNP NMR揭示了控制单重态与三重态互变的因素,并提出了生物地磁导航可能依赖的化学机制。腔吸收与单分子光谱的运用,从技术上提高了实验装置的灵敏度并降低检测限。主要介绍黄素体系电子转移过程研究所运用的各种光谱手段与取得的成果,并展望其未来。     

苯硝化反应中电子转移反应重组能的计算

提出了重组能的量子化学算法 ,在用CISD/6 31G基组水平上 ,得到苯硝化反应中反应物及过渡态的结构 .并计算了各自交换电子转移反应以及交叉电子转移反应的重组能 ,同实验重组能进行了比较 .计算用了Gaus sian 94程序 .从重组能的角度分析了苯硝化反应 .结果表明 ,对于NO2 + +NO2 →NO2 +NO2 + 的自交换电子转移反应 ,重组能较大 ,结论为 :在芳烃硝化反应中 ,存在以NO2 + 为氧化剂的电子转移步骤的可能性很小 ,而从动力学的角度上 ,用NO+ 作反应的氧化剂更有可能 .     

作为两个独立过程的双电子复合理论

在非稳态、高温高密度的等离子体环境下，双电子复合应作为完全独立的共振俘获和辐射衰变两个过程来处理．建议一种半经验公式计算共振俘获速率系数的方法，并对该公式进行了初步评估．给出了将该公式应用于平均原子模型求解速率方程的方法． 关键词：     

High entanglement generation and high fidelity quantum state transfer in a non-Markovian environment

This paper analyses a system of two independent qubits off-resonantly coupled to a common non-Markovian reservoir at zero temperature. Compared with the results in Markovian reservoirs, we find that much higher values of entanglement can be obtained for an initially factorized state of the two-qubit system. The maximal value of the entanglement increases as the detuning grows. Moreover, the entanglement induced by non-Markovian environments is more robust against the asymmetrical couplings between the two qubits and the reservoir. Based on this system, we also show that quantum state transfer can be implemented for arbitrary input states with high fidelity in the non-Markovian regime rather than the Markovian case in which only some particular input states can be successfully transferred.     

Effect of non-Markovianity on synchronization

We investigate the transient spontaneous quantum synchronization between two qubits interacting with a common non-Markovian environment based on a collision model. We are mainly interested in the effect of non-Markovianity on the synchronization between two qubits. We find that the non-Markovianity always delay the anti-synchronization and decrease the parameter region where the qubits get anti-synchronized. Meanwhile, we define V to characterize the visibility of synchronization and show that there is an apparent link among V, entanglement and quantum mutual information whether in the Markovian or non-Markovian regimes when the environment is in the vacuum state. Moreover, with the increase of temperature, the parameter region of the emergence of anti-synchronization and the time to get anti-synchronized in the non-Markovian regime gradually approaches that in the Markovian regime. The high temperature decreases the parameter region of the emergence of anti-synchronization in both Markovian and non-Markovian regimes, and breaks the connection among V, entanglement and quantum mutual information.     

Operator Correlations and Quantum Regression Theorem in Non-Markovian Lindblad Rate Equations

Non-Markovian Lindblad rate equations arise from alternative microscopic interactions such as quantum systems coupled to composite reservoirs, where extra degrees of freedom mediate the interaction between the system and a Markovian reservoir, as well as from systems coupled to complex structured reservoirs whose action can be well approximated by a direct sum of Markovian sub-reservoirs (Budini in Phys. Rev. A 74:053815 [2006]). The purpose of this paper is two fold. First, for both kinds of interactions we find general expressions for the system operator correlations written in terms of the Lindblad rate propagator. Secondly, we find the conditions under which a quantum regression hypothesis is valid. We show that a non-Markovian quantum regression theorem can only be granted in a stationary regime, being a necessary condition the fulfillment of a detailed balance condition. This result is independent of the underlying microscopic interaction, providing a criterion for the validity of the regression hypothesis in non-Markovian Lindblad-like master equations. As an example, we study the correlations of a two-level system coupled to different kind of reservoirs.     

Characterization of dynamical measurement's uncertainty in a two-qubit system coupled with bosonic reservoirs

We study the dynamical characteristics of the entropy-based uncertainty with regard to a pair of incompatible measurements under a bipartite qubit-system suffering from quantum decoherence induced by hierarchical environments. How non-Markovian and Markovian environments affect the dynamical behaviors of the measurement's uncertainty is revealed. We prove that the measured uncertainty of interest demonstrates a non-monotonic behavior, viz., the amount will increase initially and subsequently oscillate periodically with the growth of time in a non-Markovian regime; On the contrary, the uncertainty will inflate firstly and monotonically decrease in a Markovian regime. Noteworthily, we put forward a simple and feasible strategy to suppress the damping of the system and hence be good for decreasing the magnitude of the uncertainty, by virtue of optimal combination of pre-weak measurements and post-filtering operations. Furthermore, we explore the applications of the uncertainty relation investigated on entanglement witness and channel capacity.     

Deterministic controlled bidirectional remote state preparation in dissipative environments

It is a significant subject to explore effective quantum communication protocol and enhance the efficiency of the transmission process in noisy environments. In this paper, we investigate the bidirectional controlled remote preparation of an arbitrary single-qubit state in the presence of dissipative environments by using two EPR states as the entanglement source. We first construct the quantum circuit of our scheme by means of unitary matrix decomposition procedure, then the effects of the Markovian and non-Markovian environmental noises acting on the EPR states are considered through the analytical derivation and numerical calculations of the corresponding average fidelity. Moreover, we adopt two methods of weak measurement reversal (WMR) and detuning modulation to improve the average fidelity. Our results show that the average fidelity can be remarkably enhanced under appropriate conditions of the WMR strength and the detuning. Compared with the average fidelity behaviors in dissipative environments, it is also shown that the two methods for fidelity improvement are more efficient in the non-Markovian regime than in the Markovian regime.     

Optomechanical state transfer between two distant membranes in the presence of non-Markovian environments

The quantum state transfer between two membranes in coupled cavities is studied when the system is surrounded by non-Markovian environments. An analytical approach for describing non-Markovian memory effects that impact on the state transfer between distant membranes is presented. We show that quantum state transfer can be implemented with high efficiency by utilizing the experimental spectral density, and the performance of state transfer in non-Markovian environments is much better than that in Markovian environments, especially when the tunneling strength between the two cavities is not very large.     

与热库耦合的光学腔内三原子间的纠缠动力学

研究了与热库耦合的光学腔中三个相互作用的二能级原子间的纠缠动力学.采用拉普拉斯变换和下限共生等方法,通过数值计算,分析了原子间三体纠缠的演化以及腔场与热库间的两体纠缠演化,讨论了各耦合参数对系统纠缠演化的影响.研究结果表明:原子间纠缠在短时间内随着原子间耦合强度的增加而增加,随原子与腔场耦合强度的增加而减小,在长时极限下趋于一稳定值;体系的非马尔科夫性由原子与腔场的耦合强度以及热库的谱宽度共同决定,当热库与腔场为强耦合时,原子与腔场组成的系统遵循非马尔科夫动力学,此时随着热库谱宽的增加,原子系统由非马尔科夫性变为马尔科夫性,随着谱宽的继续增加,原子与腔场组成的系统遵循马尔科夫动力学,原子系统又表现出非马尔科夫性;调整腔场与热库的失谐可以有效抑制热库耗散对纠缠衰减的影响.     

Non-Markovian Effect in Optomechanical System

Most studies on optomechanical systems have been performed under the Markovian approximation. In this paper, we extend the study from the Markovian to the non-Markovian regime. According to the Markovian optomechanically induced transparency (OMIT) theory in Weis et al. (Science 330, 1520, 2010), we propose the non-Markovian counterpart. We find that the non-Markovianity might give rise to negative absorption, i.e., the probe field gains from the environment. By calculating the mean position of the mechanical resonator (MR), we illustrate the effect of non-Markovianity on the dynamics of the moving mirror.     

Dynamics of inner- and outer-sphere electron transfer in a polar solvent

In this paper, inner-sphere electron transfer reactions in a solvent are studied in the framework of multidimensional transition state theory. It is demonstrated that the preexponential factor essentially depends upon the interaction with the inner-sphere vibrational mode, increasing the rate of electron transfer as much as one order of magnitude. The prefactor is shown to be strongly dependent on the frequency of this vibration. At high frequencies the rate constant increases with the reorganization energy of this inner-sphere mode while at small frequencies, electron transfer is inhibited. Estimations of inner mode reorganization energies have been performed for system where it is necessary to account nonequilibrium solvent relaxation. Finally it is shown that the equilibrium approximation fails when the reaction is close to an activationless regime.