水位变化对正倒锥体冰载荷影响的离散元分析

在海冰与锥体海洋结构的相互作用过程中,潮汐水位变化时海冰作用于锥体结构的位置改变对冰载荷具有显著影响.本文采用具有粘结破碎功能的离散元方法计算海冰与锥体作用的破坏过程.同时考虑海冰上下表面温度差异对海冰强度的影响,将离散元计算冰载荷及海冰破坏模式与渤海现场实测数据进行对比验证.离散元结果表明,海冰与正锥和倒锥碰撞时均发生弯曲破坏,且冰载荷均随水线处锥径的增大而增大.在水线处锥径相同的情况下,正锥冰载荷大于倒锥冰载荷,而正锥作用下海冰的断裂长度则较小.基于离散元计算结果和渤海现场观测资料分析了海冰与正锥、倒锥作用时冰载荷和断裂长度差异的主要原因.海冰与正倒锥交界线处作用时,一般发生弯曲破坏.当冰层中心高度与正倒锥交界线的高度相同时,海冰才会发生局部挤压破碎,但冰荷载并没有明显升高.由此可见,倒锥体结构可有效降低冰载荷从而具有较好的抗冰性能.以上研究表明离散元方法可确定海冰与锥体结构作用时的海冰破碎规律和冰载荷特性,为海洋工程结构的抗冰设计提供参考依据.      

Structural dynamics of 4‐cyanobenzaldehyde in S2(ππ*) state

The excited state structural dynamics of 4‐cyanobenzaldehyde (p‐CNB) were studied by using the resonance Raman spectroscopy and the quantum mechanical calculations. The experimental A‐ and B‐band absorptions were, respectively, assigned to the major n_O → π₃* and π₂ → π₃* transitions according to the B3LYP‐TD/6‐31G(d) and CIS/6‐31G(d) computations, and the resonance Raman spectra. It was determined that the actual S₂(π₂π₃) state was in energy lower than S₃(π₁π₃), which was just opposite to the B3LYP‐TD/6‐31G(d) calculated order of the S₂(π₁π₃) and S₃(π₂π₃). The vibrational assignments were carried out for the A‐ and B‐band resonance Raman spectra. The B‐band resonance Raman intensities of p‐CNB were dominated by the C2–C3/C5–C6 symmetric stretch mode ν₈, the overtones nν₈ and their combination bands with the ring C–H bend mode ν₁₇, the C9–N10 stretch mode ν₆, the C7–O8 stretch mode ν₇ and the remaining modes. The conical intersection between S₁(n_Oπ₃) and S₂(π₂π₃) states of p‐CNB was determined at complete active space self‐consistent field (CASSCF)(8,7)/6‐311G(d,p) level of theory. The B‐band short‐time structural dynamics and the corresponding decay dynamics of p‐CNB were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. The resonance Raman spectra indicated that CI[S₁(n_Oπ₃)/S₂(π₁π₂π₃π₄)] located nearby the Franck–Condon region. The excited state decay dynamics evolving from the S_{2, FC}(π₂π₃) to the S₁(n_Oπ₃) state was proposed. Copyright © 2013 John Wiley & Sons, Ltd.     

光腔与扩压器的一体化优化数值模拟

采用数值模拟方法对化学氧碘化学激光器光腔通道、超声速扩压器一体化方案的优化展开研究,对扩压器的角度、构型、背压等参数对扩压性能的影响以及对光腔内流场的影响进行计算和分析。研究结果表明:传统的直接扩散型以及平直段+扩散段型的超声速扩压器,抵抗背压影响的能力较弱,且光腔出口处静压急剧升高,影响了光腔内的流场;通过在平直段+扩散段型的超声速扩压器的平直段部分,插入数片楔形体,可以将扩压器的工作背压提升33%以上,且可以有效地隔绝扩压器对光腔内流场的不利影响,从而使光腔下游的逆压梯度大大降低;同时,由于缩短了扩压器的长度,扩压器的总压损失明显降低,冷流状态下的总压恢复系数达到0.484。     

基于双层微透镜阵列的移动视差式立体显示屏

受限于微透镜的数值孔径和像差问题,目前移动视差式立体显示屏存在多视场空间、视场区之间存在视场跳变、主视场空间角度小、显示效果模糊等问题.本文基于离散采样思想,分析了移动视差型三维显示系统的工作机理,结合加工工艺,设计了复合曲面反射层的双层微透镜阵列屏.仿真结果表明:所设计显示屏的视场观看空间角可提升到60°,相对于传统的三维显示屏,双层微结构显示屏可有效提高视场角和显示性能.     

Photodeactivation paths in norbornadiene

The first high level ab initio quantum‐chemical calculations of potential energy surfaces (PESs) for low‐lying singlet excited states of norbornadiene in the gas phase are presented. The optimization of the stationary points (minima and conical intersections) and the recalculation of the energies were performed using the multireference configuration interaction with singles (MR‐CIS) and the multiconfigurational second‐order perturbation (CASPT2) methods, respectively. It was shown that the crossing between valence V₂ and Rydberg R₁ states close to the Franck–Condon (FC) point permits an easy population switch between these states. Also, a new deactivation path in which the doubly excited state with (π₃)² configuration (DE) has a prominent role in photodeactivation from the R₁ state due to the R₁/DE and the DE/V₁ conical intersections very close to the R₁ and DE minima, respectively, was proposed. Subsequent deactivation from the V₁ to the ground state goes through an Olivucci–Robb‐type conical intersection that adopts a rhombic distorted geometry. The deactivation path has negligible barriers, thereby making ultrafast radiationless decay to the ground state possible. © 2013 Wiley Periodicals, Inc.     

Initiation of detonation by conical projectiles

Initiation of detonation by a hypersonic conical projectile launched into a combustible gas mixture is investigated. From analytic considerations of the flowfield, energetic and kinetic limits are proposed to predict the conditions required to initiate an oblique detonation wave in the mixture. To experimentally investigate these limits, projectiles with cone half angles varying from 15° to 60° were launched into a stoichiometric mixture of hydrogen/oxygen with 70% argon dilution at initial pressure between 10 and 200 kPa. The projectiles were launched from a combustion-driven gas gun at velocities as great as 2.5 km/s (corresponding to 150% of the Chapman Jouguet velocity). Pictures of the flowfields generated by the projectiles were taken via schlieren photography. Five combustion regimes could be observed about the projectile ranging from a prompt and delayed oblique detonation wave formation, combustion instabilities, a wave splitting, and an inert shock wave. The two theoretical limits provide a means to interpret the observed flowfield regimes and are in satisfactory agreement with the experimental results.     

Bridged Stilbenes: AIEgens Designed via a Simple Strategy to Control the Non‐radiative Decay Pathway

To broaden the application of aggregation‐induced emission (AIE) luminogens (AIEgens), the design of novel small‐molecular dyes that exhibit high fluorescence quantum yield (Φ_fl) in the solid state is required. Considering that the mechanism of AIE can be rationalized based on steric avoidance of non‐radiative decay pathways, a series of bridged stilbenes was designed, and their non‐radiative decay pathways were investigated theoretically. Bridged stilbenes with short alkyl chains exhibited a strong fluorescence emission in solution and in the solid state, while bridged stilbenes with long alkyl chains exhibited AIE. Based on this theoretical prediction, we developed the bridged stilbenes BPST[7] and DPB[7], which demonstrate excellent AIE behavior.     

Direct Observation of Aggregation‐Induced Emission Mechanism

The mechanism of aggregation‐induced emission, which overcomes the common aggregation‐caused quenching problem in organic optoelectronics, is revealed by monitoring the real time structural evolution and dynamics of electronic excited state with frequency and polarization resolved ultrafast UV/IR spectroscopy and theoretical calculations. The formation of Woodward–Hoffmann cyclic intermediates upon ultraviolet excitation is observed in dilute solutions of tetraphenylethylene and its derivatives but not in their respective solid. The ultrafast cyclization provides an efficient nonradiative relaxation pathway through crossing a conical intersection. Without such a reaction mechanism, the electronic excitation is preserved in the molecular solids and the molecule fluoresces efficiently, aided by the very slow intermolecular charge and energy transfers due to the well separated molecular packing arrangement. The mechanisms can be general for tuning the properties of chromophores in different phases for various important applications.     

A Conical Intersection Controls the Deactivation of the Bacterial Luciferase Fluorophore

The photophysics of flavins is highly dependent on their environment. For example, 4a‐hydroxy flavins display weak fluorescence in solution, but exhibit strong fluorescence when bound to a protein. To understand this behavior, we performed temperature‐dependent fluorescent studies on an N(5)‐alkylated 4a‐hydroxy flavin: the putative bacterial luciferase fluorophore. We find an increase in fluorescence quantum yield upon reaching the glass transition temperature of the solvent. We then employ multiconfigurational quantum chemical methods to map the excited‐state deactivation path of the system. The result reveals a shallow but barrierless excited state deactivation path that leads to a conical intersection displaying an orthogonal out‐of‐plane distortion of the terminal pyrimidine ring. The intersection structure readily explains the observed spectroscopic behavior in terms of an excited‐state barrier imposed by the rigid glass cavity.     

激光动态外锥折射实验研究

根据双轴晶体的锥形折射效应，提出锥角可控的动态外锥折射以及一种实现外锥折射的新方法；选用ＫＮｂＯ３晶体进行实验，不仅观察到外锥折射，而且实现了锥角在０°～８°范围内的外锥折射扫描控制