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.     

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.     

锥型热声谐振管内非线性声场的数值模拟研究

从声学角度出发,考虑粘性耗散、非线性效应及管型结构变化的影响,利用伽辽金法,对锥型热声谐振管内的一维声场进行了数值模拟研究,对谐振管结构参数对声场的影响进行了分析,给出了锥型管内压比随谐振管结构参数变化的规律,通过与圆柱型直管的比较,揭示了锥型管在抑制谐波及提高压比等方面的优越性。     

Mechanistic Photodissociation of Glycolaldehyde: Insights from Ab Initio and RRKM Calculations

Herein we report a theoretical study on mechanistic photodissociation of glycolaldehyde, HOCH₂CHO. Equilibrium structures, transition states, and intersection structures for the α‐C? C and ‐C? H bond fissions and the β‐C? O bond fission in the excited states are determined by the complete active space self‐consistent field (CASSCF) method. Based on the CASSCF optimized structures, the potential energy profiles for the dissociations are refined by performing single‐point calculations using the multi‐state multi‐reference CASSCF second order perturbation (MS‐MR‐CASPT2) method. With a low excitation energy of 280–340 nm, the T₁ α‐C? C and β‐C? O bond fissions following intersystem crossing from the S₁ state are the predominant and comparable channels, whereas the α‐C? H bond fissions both in the S₁ and in the T₁ states are nearly prohibited due to the relevant high barriers. The rate constants for the T₁ α‐C? C and β‐C? O bond fissions are also calculated by RRKM theory. Furthermore, the S₀ reactions can occur as a consequence of intersystem crossing via T₁/S₀ intersection points resulting from the T₁ C? C and C? O bond cleavages. This photodissociation mechanism is consistent with recent experimental studies.     

Flow produced in a conical container by a rotating endwall

Numerical calculations have been carried out for flow in a truncated cone generated by rotation of one endwall. For both convergent (radius increasing with approach to the rotating endwall) and divergent geometries, vortex breakdown is suppressed beyond a certain angle of inclination of the sidewall. At the same time Moffat eddies of increasing strength and extent appear in the corner between the sidewall and the non-rotating endwall. For the divergent geometry, a zone of recirculation appears on the sidewall and eventually merges with the Moffat eddies. The flow phenomena identified from streamline patterns are consistent with the calculated variation of pressure around the periphery of the computational domain.     

Modulating the Photochemistry of Bipyridylic Compounds by Symmetric Substitutions

A quantum electronic study of the effect of substituents on (2,2′‐bipyridyl)‐3,3′‐diol and (2,2′‐bipyridyl)‐3,3′‐diamine is presented. A large difference in the photochemical behavior between the original and the substituted selected systems is expected. For the sake of simplicity, the study is restricted to the symmetrically bi‐substituted compounds: fluorine, the more electronegative atom and thus a strong σ‐acceptor but also a weak π‐donor group, and NO₂, a strong π‐acceptor substituent. Among the large set of compounds studied, two receive special attention: 5,5′‐dinitro‐(2,2′‐bipyridyl)‐3,3′‐diamine and 6,6′‐difluoro‐(2,2′‐bipyridyl)‐3,3′‐diol. While in the former case the nitro substitution transforms (2,2′‐bipyridyl)‐3,3′‐diamine, previously suggested to behave as a photomemory material, into a simple fluorescent species, the latter substitution turns (2,2′‐bipyridyl)‐3,3′‐diol into a fresh new candidate for a photomemory device.     

Numerical simulation of rock fragmentation during cutting by conical picks under confining pressure

In this article, the effect of confining pressure on rock fragmentation process during cutting was investigated by numerical simulation with a discrete element method (DEM). Four kinds of sandstones with different physical properties were simulated in the rock cutting models under different confining pressures. The rock fragmentation process, the cutting force, and the specific energy under different confining pressures were analyzed. With the increase in confining pressure and rock strength, the vertical propagation of cracks was restrained. Rock samples were compacted and strengthened by confining pressure resulting in the increase of the cutting force. The specific energy of rock cutting linearly increased with the increase of the confining pressure ratio.     

Decay Dynamics of N,N-Dimethylthioacetamide in S3(ππ*) State (cited: 1)

The decay dynamics of N,N-dimethylthioacetamide after excitation to the S₃(ππ^*) state was studied by using the resonance Raman spectroscopy and complete active space selfconsistent field method calculations. The UV-absorption and vibrational spectra were assigned. The A-band resonance Raman spectra were obtained in acetonitrile, methanol and water with the laser excitation wavelengths in resonance with the first intense absorption band to probe the Franck-Condon region structural dynamics. The CASSCF calculations were carried out to determine the excitation energies and optimized structures of the lowerlying singlet states and conical intersection point. The A-band structural dynamics and the corresponding decay mechanism were obtained by the analysis of the resonance Raman intensity pattern and the CASSCF calculated structural parameters. The major decay channel of _3,FC(ππ^*)→S₃(ππ^*)/S₁(nπ^*)→_{1(nπ^*) is proposed.}     

State to State Photodissociation Dynamics of Vibrationally Excited D2O in B Band

The state-to-state photodissociassion dynamics for the B band of D₂O have been explored from quantum dynamical calculations including the electronic ~X and ~B states. The calculations were carried out using a Chebyshev real wave packet method. The calculated absorption spectra, product state distributions, and branching ratios from different initial vibrational states show di?erent dynamic features, due to the different shapes of the vibrational wavefunctions. The initial bending mode (0,1,0) generates two lobes with a shallow minimum on the absorption spectrum and a slight inverted vibrational population of OD(~X )product at high total energies. The rotational state distributions of OD(~X , v=0) product are highly inverted and depend weakly on the initial state and total energy. On the other hand, the ro-vibrational distributions of OD(A~) product strongly oscillate with the total energy, which are dominated by the long-living resonances and depend sensitively on the potential surfaces. The antisymmetric stretching mode (0,0,1) has large OD( ~ A)/OD(~X ) branching ratios at high total energies, which indicates that the B band dissociation proceeds mainly via the adiabatic pathway in some cases.