Analyzing Grid-Based Direct Quantum Molecular Dynamics Using Non-Linear Dimensionality Reduction

Grid-based schemes for simulating quantum dynamics, such as the multi-configuration time-dependent Hartree (MCTDH) method, provide highly accurate predictions of the coupled nuclear and electronic dynamics in molecular systems. Such approaches provide a multi-dimensional, time-dependent view of the system wavefunction represented on a coordinate grid; in the case of non-adiabatic simulations, additional information about the state populations adds a further layer of complexity. As such, wavepacket motion on potential energy surfaces which couple many nuclear and electronic degrees-of-freedom can be extremely challenging to analyse in order to extract physical insight beyond the usual expectation-value picture. Here, we show that non-linear dimensionality reduction (NLDR) methods, notably diffusion maps, can be adapted to extract information from grid-based wavefunction dynamics simulations, providing insight into key nuclear motions which explain the observed dynamics. This approach is demonstrated for 2-D and 9-D models of proton transfer in salicylaldimine, as well as 8-D and full 12-D simulations of cis-trans isomerization in ethene; these simulations demonstrate how NLDR can provide alternative views of wavefunction dynamics, and also highlight future developments.     

量子控制论在化学中的应用

控制量子现象是化学研究中的一个重要目标,量子控制论对实现该目标具有积极的指导意义.本文综述了量子控制论在化学中的应用及其进展,重点分析了量子相干控制、量子优化控制、闭环学习控制和能控性观念在化学研究中的应用,介绍了它们的研究现状,并对其未来研究进行了展望.     

Low‐Temperature Thermal Rate Constants for the Water Formation Reaction H2+OH from Rigorous Quantum Dynamics Calculations

Thermal rate constants for the prototypical water‐forming reaction H₂+OH→H+H₂O were obtained for temperatures between 150 K and 600 K by rigorous quantum dynamics calculations including all degrees of freedom. Results are reported for a recent, highly accurate neural network potential (NN1) and compared to results obtained on a previous, semi‐empirical potential (SE). The rate constants computed on both potentials significantly differ in their temperature dependence, and differences of over one order of magnitude in the rates were found. The rate constants computed for the NN1 potential compare very well to experimental work. Furthermore, the influence of overall rotation is discussed for the title reaction. While previous close‐coupling simulations were limited to thermal rate constants above room temperature, we report rate constants for temperatures as low as 250 K. The high‐level results reported here provide an accurate benchmark for the development of approximate methods for the calculation of thermal as well as microcanonical rate constants.     

Ultrafast Carrier Dynamics in CdSe/CdS/ZnS Quantum Dots

The intra- and inter-band relaxation dynamics of CdSe/CdS/ZnS core/shell/shell quantum dots are investigated with the aid of time-resolved nonlinear transmission spectra which are obtained using femtosecond pump-probe technique. By selectively exciting the core and shell carrier, the dynamics are studied in detail. Carrier relaxation is found faster in the conduction band of the CdS shell (about 130 fs) than that in the conduction band of the CdSe core (about 400 fs). From the experiments it is distinctly demonstrated the existence of the defect states in the interface between the CdSe core and the CdS shell, indicating thatultrafast spectroscopy might be a suitable tool in studying interface and surface morphology properties in nanosystems.     

Quantum tunneling effect in entanglement dynamics

Quantum tunneling effect in entanglement dynamics between two coupled particles with separable Gaussian initial state is investigated using entangled trajectory molecular dynamics method in terms of the reduced‐density linear entropy. It has been presented through showing distinguish contribution of single trajectory to linear entropy between classical trajectory and entangled trajectory with same initial state. We find that quantum tunneling effect makes single trajectory's contribution remarkably decrease under quantum dynamics compared to classical dynamics. The nonlocality of quantum entanglement is presented, and the energy transfer between two coupled particles through quantum correlations and classical ones is also discussed in the end. © 2015 Wiley Periodicals, Inc.     

Quantum Control of Gas‐Phase and Liquid‐Phase Femtochemistry

Active control of chemical reactions on a microscopic (molecular) level, that is, the selective breaking or making of chemical bonds, is an old dream. However, conventional control agents used in chemical synthesis are macroscopic variables such as temperature, pressure or concentration, which gives no direct access to the quantum‐mechanical reaction pathway. In quantum control, by contrast, molecular dynamics are guided with specifically designed light fields. Thus it is possible to efficiently and selectively reach user‐defined reaction channels. In the last years, experimental techniques were developed by which many breakthroughs in this field were achieved. Femtosecond laser pulses are manipulated in so‐called pulse shapers to generate electric field profiles which are specifically adapted to a given quantum system and control objective. The search for optimal fields is guided by an automated learning loop, which employs direct feedback from experimental output. Thereby quantum control over gas‐phase as well as liquid‐phase femtochemical processes has become possible. In this review, we first discuss the theoretical and experimental background for many of the recent experiments treated in the literature. Examples from our own research are then used to illustrate several fundamental and practical aspects in gas‐phase as well as liquid‐phase quantum control. Some additional technological applications and developments are also described, such as the automated optimization of the output from commercial femtosecond laser systems, or the control over the polarization state of light on an ultrashort timescale. The increasing number of successful implementations of adaptive learning techniques points at the great versatility of computer‐guided optimization methods. The general approach to active control of light–matter interaction has also applications in many other areas of modern physics and related disciplines.     

Ultrafast Electron Transfer with Symmetrical Quasi-classical Dynamics based on Mapping Hamiltonian and Quantum Dynamics based on ML-MCTDH

Symmetrical quasi-classical (SQC) method based on mapping Hamiltonian is an efficient approach that is potentially useful to treat the nonadiabatic dynamics of very large systems. We try to evaluate the performance of this method in the ultrafast electron transfer processes involving a few of electronic states and a large number of vibrational modes. The multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) method was used to get the accurate dynamical results for benchmark. Although the population dynamics in the longtime limit show differences in the ML-MCTDH and SQC calculations, the SQC method gives acceptable results.     

Quantum evolution speed and its limit in the driven double-well system

We investigate quantum evolution speed in the driven double-well system using the entangled trajectory molecular dynamics method. We emphasize not only the evolution speed of the quantum state but also its limit according to different definitions. The Wasserstein 1-distance is used to quantify the distance between distinguishable quantum states in the phase space, the quantum speed limit based on the geometry has been shown to be the strictest one. The single trajectory's contribution to the quantum speed limit is discussed, which is related to both the time evolution of the trajectory and its position in the total Wigner function. The resonance and chaos strongly enhance the evolution speed and its limit in the driven double-well system. The resonance effect makes a large proportion of representative points pass through the well as a whole, nevertheless, the chaos makes the Wigner function disperse in the phase space.     

Local Control Theory in Trajectory Surface Hopping Dynamics Applied to the Excited‐State Proton Transfer of 4‐Hydroxyacridine

The application of local control theory combined with nonadiabatic ab initio molecular dynamics to study the photoinduced intramolecular proton transfer reaction in 4‐hydroxyacridine was investigated. All calculations were performed within the framework of linear‐response time‐dependent density functional theory. The computed pulses revealed important information about the underlying excited‐state nuclear dynamics highlighting the involvement of collective vibrational modes that would normally be neglected in a study performed on model systems constrained to a subset of the full configuration space. This study emphasizes the strengths of local control theory for the design of pulses that can trigger chemical reactions associated with the population of a given molecular excited state. In addition, analysis of the generated pulses can help to shed new light on the photophysics and photochemistry of complex molecular systems.     

Quantum interference effects in the Br2 electronic predissociation: Dependence upon the molecular properties

The occurrence of quantum interference in the Br₂ electronic predissociation has been observed for the first time. It is also shown that the quantum interference effects are strongly dependent upon the representation of the molecular properties, such as the kinetic coupling and the transition dipole moment. The fast Fourier transform method implemented within the wave packet formalism was used to simulate the time evolution of the molecular system under the influence of single monochromatic ultrashort laser pulses. The quantum interference has been inferred from the oscillatory behavior of the autocorrelation functions, which have also been used to calculate the cross-sections, the branching ratios, and the selectivity. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Quantum Master Equation Approach to Singlet Fission Dynamics in Pentacene Linear Aggregate Models: Size Dependences of Excitonic Coupling Effects

The singlet fission (SF) dynamics of pentacene linear aggregate models are investigated using the quantum master equation method by focusing on the Frenkel excitonic (FE) coupling effects on the SF rate and double triplet (TT) yield as well as on their aggregate size dependences. It is found that for the dimer model, unrealistically large FE couplings are needed to provide significant effects on the SF dynamics, while for the larger aggregate models a realistic FE coupling causes significant variations in the SF dynamics: as increasing the aggregate size, the SF rate rapidly increases, attains the maximum at 8-mer (~3 times enhancement as compared to the non-FE-coupling case) and then decreases, approaching a stationary value after 12-mer, although the stationary TT yield at 20-mer remains slightly smaller than that in the non-FE-coupling case. These features are explained based on the relative relaxation factors between the adiabatic exciton states. The present results contribute to constructing the design guidelines for highly efficient SF aggregates. © 2018 Wiley Periodicals, Inc.     

A Brief Overview of Some Physical Studies on the Relaxation Dynamics and Förster Resonance Energy Transfer of Semiconductor Quantum Dots

This article highlights some physical studies on the relaxation dynamics and Förster resonance energy transfer (FRET) of semiconductor quantum dots (QDs) and the way these phenomena change with size, shape, and composition of the QDs. The understanding of the excited‐state dynamics of photoexcited QDs is essential for technological applications such as efficient solar energy conversion, light‐emitting diodes, and photovoltaic cells. Here, our emphasis is directed at describing the influence of size, shape, and composition of the QDs on their different relaxation processes, that is, radiative relaxation rate, nonradiative relaxation rate, and number of trap states. A stochastic model of carrier relaxation dynamics in semiconductor QDs was proposed to correlate with the experimental results. Many recent studies reveal that the energy transfer between the QDs and a dye is a FRET process, as established from 1/d⁶ distance dependence. QD‐based energy‐transfer processes have been used in applications such as luminescence tagging, imaging, sensors, and light harvesting. Thus, the understanding of the interaction between the excited state of the QD and the dye molecule and quantitative estimation of the number of dye molecules attached to the surface of the QD by using a kinetic model is important. Here, we highlight the influence of size, shape, and composition of QDs on the kinetics of energy transfer. Interesting findings reveal that QD‐based energy‐transfer processes offer exciting opportunities for future applications. Finally, a tentative outlook on future developments in this research field is given.     

Halogen Bonding in Haspin-Halogenated Tubercidin Complexes: Molecular Dynamics and Quantum Chemical Calculations

Haspin, an atypical serine/threonine protein kinase, is a potential target for cancer therapy. 5-iodotubercidin (5-iTU), an adenosine derivative, has been identified as a potent Haspin inhibitor in vitro. In this paper, quantum chemical calculations and molecular dynamics (MD) simulations were employed to identify and quantitatively confirm the presence of halogen bonding (XB), specifically halogen∙∙∙π (aromatic) interaction between halogenated tubercidin ligands with Haspin. Consistent with previous theoretical finding, the site specificity of the XB binding over the ortho-carbon is identified in all cases. A systematic increase of the interaction energy down Group 17, based on both quantum chemical and MD results, supports the important role of halogen bonding in this series of inhibitors. The observed trend is consistent with the experimental observation of the trend of activity within the halogenated tubercidin ligands (F < Cl < Br < I). Furthermore, non-covalent interaction (NCI) plots show that cooperative non-covalent interactions, namely, hydrogen and halogen bonds, contribute to the binding of tubercidin ligands toward Haspin. The understanding of the role of halogen bonding interaction in the ligand–protein complexes may shed light on rational design of potent ligands in the future.     

Triplet-triplet Annihilation Dynamics of Naphthalene

Triplet-triplet annihilation (TTA) is a spin-allowed conversion of two triplet states into one singlet excited state, which provides an efficient route to generate a photon of higher frequency than the incident light. Multiple energy transfer steps between absorbing (sensitizer) and emitting (annihilator) molecular species are involved in the TTA based photon upconversion process. TTA compounds have recently been studied for solar energy applications, even though the maximum upconversion efficiency of 50 % is yet to be achieved. With the aid of quantum calculations and based on a few key requirements, several design principles have been established to develop the well-functioning annihilators. However, a complete molecular level understanding of triplet fusion dynamics is still missing. In this work, we have employed multi-reference electronic structure methods along with quantum dynamics to obtain a detailed and fundamental understanding of TTA mechanism in naphthalene. Our results suggest that the TTA process in naphthalene is mediated by conical intersections. In addition, we have explored the triplet fusion dynamics under the influence of strong light-matter coupling and found an increase of the TTA based upconversion efficiency.     

Localization and Dynamics of Long‐Lived Excitations in Colloidal Semiconductor Nanocrystals with Dual Quantum Confinement

Semiconductor nanocrystals consisting of a quantum dot (QD) core and a quantum well (QW) shell, where the QD and QW are separated by a tunneling barrier, offer a unique opportunity to engineer the photophysical properties of individual nanostructures. Using the thicknesses of the corresponding layers, the excitons of the first and second excited states can be separated spatially, localizing one state to the QD and the other to the QW. Thus the wave function overlap of the two states can be minimized, suppressing non‐radiative thermalization between the two wells, which in turn leads to radiative relaxation from both states. The molecular analogy to such dual emission would be the inhibition of internal conversion, a special case that violates Kasha′s rule. Using nanosecond time‐resolved spectroscopy of QDQW CdSe/ZnS onion‐like nanocrystals, an intermediate regime of exciton separation and suppressed thermalization is identified where the non‐radiative relaxation of the higher‐energy state is slowed, but not completely inhibited. In this intermediate thermalization regime, the temporal evolution of the delayed emission spectra resulting from trapped carriers mimic the dynamics of such states in nanocrystals that consist of only a QD core. In stark contrast, when a higher‐energy metastable state exists in the QW shell due to strongly suppressed interwell thermalization, the spectral dynamics of the long‐lived excitations in the QD and QW, which are spectrally distinct, are amplified and differ from each other as well as from those in the core‐only nanocrystals. This difference in spectral dynamics demonstrates the utility of exploiting well‐defined exciton localization to study the nature and spatial dependence of the intriguing photophysics of colloidal semiconductor nanocrystals, and illustrates the power of nanosecond gated luminescence spectroscopy in illuminating complex relaxation dynamics which are entirely masked in steady‐state or ultrafast spectroscopy.     

共振论的应用及量子化学探讨

共振论自20世纪30年代鲍林（Pauling L）提出以来,其在有机化学中有着较为广泛的应用。本文简述了共振论的产生及有关的基础知识,其中用共振论观点解释了一些用经典结构理论所不能说明的有机化合物的性质,并且用Gaussian98程序对其进行了量子化学探讨。     

Accurate Quantum Dynamics of the Simplest Isomerization System Involving Double-H Transfer

We perform accurate quantum dynamics calculations on the isomerization of vinylidene-acetylene. Large-scale parallel computations are accomplished by an efficient theoretical scheme developed by our group, in which the basis functions are customized for the double-H transfer process. The \begin{document}$ A_1' $\end{document} and \begin{document}$ B_2'' $\end{document} vinylidene and delocalization states are obtained. The peaks recently observed in the cryo-SEVI spectra are analyzed, and very good agreement for the energy levels is achieved between theory and experiment. The discrepancies of energy levels between our calculations and recent experimental cryo-SEVI spectra are of similar magnitudes to the experimental error bars, or \begin{document}$ \le $\end{document}30 cm\begin{document}$ ^{-1} $\end{document} excluding those involving the excitation of the CCH\begin{document}$ _2 $\end{document} scissor mode. A kind of special state, called the isomerization state, is revealed and reported, which is characterized by large probability densities in both vinylidene and acetylene regions. In addition, several states dominated by vinylidene character are reported for the first time. The present work would contribute to the understanding of the double-H transfer.