Exploring Potential Energy Surfaces for Aggregation‐Induced Emission—From Solution to Crystal

Aggregation‐induced emission (AIE) is a phenomenon where non‐luminescent compounds in solution become strongly luminescent in aggregate and solid phase. It provides a fertile ground for luminescent applications that has rapidly developed in the last 15 years. In this review, we focus on the contributions of theory and computations to understanding the molecular mechanism behind it. Starting from initial models, such as restriction of intramolecular rotations (RIR), and the calculation of non‐radiative rates with Fermi's golden rule (FGR), we center on studies of the global excited‐state potential energy surfaces that have provided the basis for the restricted access to a conical intersection (RACI) model. In this model, which has been shown to apply for a diverse group of AIEgens, the lack of fluorescence in solution comes from radiationless decay at a CI in solution that is hindered in the aggregate state. We also highlight how intermolecular interactions modulate the photophysics in the aggregate phase, in terms of fluorescence quantum yield and emission color.     

Theoretical Investigation of the Reaction Mechanism of the Photoisomerization of 1,2‐Dihydro‐1,2‐azaborine

The photoisomerization of 1,2‐dihydro‐1,2‐azaborine was investigated by high‐level multireference ab initio and density functional theory calculations. The intermediates (IMs) and transition states (TSs) on the S₀ and S₁ states were optimized using the state‐averaged complete active space self‐consistent field method. The multireference configuration interaction method with the Davidson correction was used to obtain accurate energetics. Moreover, the conical intersections (CIs), which play a crucial role in photoisomerization, were also optimized. On the basis of the calculation results, the most favorable proposed reaction pathway is as follows: reactant→Franck‐Condon region→TS₁→CI→IM₀→TS_0P→product. The product was not directly formed through the CI, and the IM₀ existed on the S₀ state. These results show that the isomerization of 1,2‐dihydro‐1,2‐azaborine involves both photoreactions and thermal reactions. The calculated results clarify recent experimental observations.     

Perturbing π-clouds with Substituents to Study the Effects on Reaction Dynamics of gauche-1,3-Butadiene to Bicyclobutane Electrocyclization

The conical intersection (CI) governs the ultra-fast relaxation of excited states in a radiationless manner and are observed mainly in photochemical processes. In the current work, we investigated the effects of substituents on the reaction dynamics for the conversion of gauche-1,3-butadiene to bicyclobutane via photochemical electrocyclization. We incorporated both electron withdrawing (−F) and donating (−CH₃) groups in the conjugated system. In our study, we optimized the minimum energy conical intersection (MECI) geometries using the multi-configurational state-averaged CASSCF approach, whereas, to study the ground state reaction pathways for the substituted derivatives, dispersion corrected, B3LYP-D3 functional was used. The non-adiabatic surface hopping molecular dynamics simulations were performed to observe the behaviour of electronic states involved throughout the photoconversion process. The results obtained from the multi-reference second-order perturbation correction of energy at the XMS-CASPT2 level of theory, topography analysis, and non-adiabatic dynamics suggest that the −CH₃ substituted derivatives can undergo faster thermal conversion to the product in the ground state with a smaller activation energy barrier compared to −F substituted derivative. Our study also reveals that the GBUT to BIBUT conversion follows both conrotatory and disrotatory pathways, whereas, on substitution with −F or −CH₃, the conversion proceeds via the conrotatory pathway.     

Photochemical Hydrogen Evolution at Metal Centers Probed with Hydrated Aluminium Cations,Al+(H2O)n,n=1–10

Hydrated aluminium cations have been investigated as a photochemical model system with up to ten water molecules by UV action spectroscopy in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Intense photodissociation was observed starting at 4.5 eV for two to eight water molecules with loss of atomic hydrogen, molecular hydrogen and water molecules. Quantum chemical calculations for n=2 reveal that solvation shifts the intense 3s–3p excitations of Al⁺ into the investigated photon energy range below 5.5 eV. During the photochemical relaxation, internal conversion from S₁ to T₂ takes place, and photochemical hydrogen formation starts on the T₂ surface, which passes through a conical intersection, changing to T₁. On this triplet surface, the electron that was excited to the Al 3p orbital is transferred to a coordinated water molecule, which dissociates into a hydroxide ion and a hydrogen atom. If the system remains in the triplet state, this hydrogen radical is lost directly. If the system returns to singlet multiplicity, the reaction may be reversed, with recombination with the hydroxide moiety and electron transfer back to aluminium, resulting in water evaporation. Alternatively, the hydrogen radical can attack the intact water molecule, forming molecular hydrogen and aluminium dihydroxide. Photodissociation is observed for up to n=8. Clusters with n=9 or 10 occur exclusively as HAlOH⁺(H₂O)_n-1 and are transparent in the investigated energy range. For n=4–8, a mixture of Al⁺(H₂O)_n and HAlOH⁺(H₂O)_n-1 is present in the experiment.     

Modulating ion current rectification generating high energy output in a single glass conical nanopore channel by concentration gradient

Inspired by biological systems that have the inherent skill to generate considerable bioelectricity from the salt content in fluids with highly selective ion channels and pumps on cell membranes,herein,a fully abiotic,single glass conical nanopores energy-harvesting is demonstrated.Ion current rectification(ICR)in negatively charged glass conical nanopores is shown to be controlled by the electrolyte concentration gradient depending on the direction of ion diffusion.The degree of ICR is enhanced with the increasing forward concentration difference.An unusual rectification inversion is observed when the concentration gradient is reversely applied.The maximum power output with the individual nanopore approaches10~4pW.This facile and cost-efficient energy-harvesting system has the potential to power tiny biomedical devices or construct future clean-energy recovery plants.     

杭州大剧院风压分布的风洞试验研究

杭州大剧院外观造型新颖独特，由一个近似为椭球的双曲面屋盖和一个倒置的圆锥面玻璃幕墙相交形成大剧院的主体建筑的外轮廓．本文结合该主体结构的抗风设计要求，制作了1：200刚性模型进行结构表面脉动风压平均风压分布的风洞试验研究，详细介绍了风洞试验及数据处理方法，讨论了在不同风向角下椭球面屋盖和圆锥面玻璃幕墙的风压分布．为了便于整体结构设计，本文根据结构的实际情况对椭球面和圆锥面进行分块并给出相应的分块风压数据，最后根据各风向角下的风压分布特征给出了整体结构抗风设计的最不利风向角．     

胀锚型锚栓锚固破坏及承载力研究

混凝土基材锥体受拉破坏是后锚固锚栓受拉的基本破坏形式，采用混凝土破坏准则和弹性力学方法，推导了胀锚型锚栓基于混凝土基材破坏的抗拔极限承载力简化计算公式．通过对不同混凝土强度的极限状态数值分析，发现基材锚固破坏锥面底部直径R与有效锚固深度he为近似比值关系。与试验的对比结果表明，简化计算方法精度满足工程需要，和多种试验测试结果相当吻合。     

Excited-state surfaces of ethylene from the B13 strong-correlation density functional

The energy surfaces of the ground and low-lying excited states of ethylene are challenging tests of multi-reference electronic structure methods. A variety of multi-reference wavefunction theories have been applied to this problem and the ensuing photochemistry has been well studied. Density-functional methods, however, have been less successful. In this work, the ‘B13’ strong-correlation density functional is used to generate multi-reference orbitals for the computation of the three lowest-lying singlet states. We explore the states and energies as a function of torsion angle, and as a function of the pyramidalisation angle with respect to the twisted orthogonal structure. The former features an avoided crossing at the orthogonal structure; the latter a C_s slice through a conical intersection. Both features are well reproduced by our B13 method.     

离心压气机叶片扩压器的不稳定流动特征

本文用高频响应的热线风速仪及压力传感器作为测量仪器,与磁带记录仪及CF-920动态信号分析仪一起,组成测量及分析系统,并用该系统对离心压气机带叶片扩压器时的流动脉动进行了测量,得出了流体脉动的时间和空间特征.文中给出了失速波形及失速参数随流量的详细变化.本文装置上产生三团失速,流量减小过程中。失速团以2.2%～7%的叶轮转动速度旋转.转速变化时,失速现象的演变过程并不发生变化.失速时,叶片扩压器前缘附近的流动最为恶化,流体脉动幅度较大,气流角的变化剧烈.