Designing spirobifullerene core based three-dimensional cross shape acceptor materials with promising photovoltaic properties for high-efficiency organic solar cells

The development of organic electron acceptor materials is one of the key factors for realizing high-performance organic solar cells (OSCs). Nonfullerene electron acceptors, compared to traditional fullerene acceptor materials, have gained much impetus owing to their better optoelectronic tunabilities and lower cost, as well as higher stability. Therefore, 5 three-dimensional (3D) cross-shaped acceptor materials having a spirobifullerene core flanked with 2,1,3-benzothiadiazole are designed from a recently synthesized highly efficient acceptor molecule SF(BR) ₄ and are investigated in detail with regard to their use as acceptor molecules in OSCs. The density functional theory (DFT) and time-dependent DFT (TDDFT) calculations have been performed for the estimation of frontier molecular orbital (FMO) analysis, density of states analysis, reorganization energies of electron and hole, dipole moment, open-circuit voltage, photo-physical characteristics, and transition density matrix analysis. In addition, the structure-property relationship is studied, and the influence of end-capped acceptor modifications on photovoltaic, photo-physical, and electronic properties of newly selected molecules ( H1-H5 ) is calculated and compared with reference ( R ) acceptor molecule SF(BR) ₄ . The structural tailoring at terminals was found to effectively tune the FMO band gap, energy levels, absorption spectra, open-circuit voltage, reorganization energy, and binding energy value in selected molecules H1 to H5 . The 3D cross-shaped molecules H1 to H5 suppress the intermolecular aggregation in PTB7-Th blend, which leads to high efficiency of acceptor material H1 to H5 in OSCs. Consequently, better optoelectronic properties are achieved from designed molecules H1 to H5 . It is proposed that the conceptualized molecules are superior than highly efficient spirobifullerene core-based SF(BR) ₄ acceptor molecules and, thus, are recommended to experiments for future developments of highly efficient solar cells.     

微波瑞利散射法测定空气电火花激波等离子体射流的时变电子密度

大气压空气电火花激波等离子体射流的电子密度在亚微秒时间尺度上瞬变,其电子密度的测定很难.基于微波瑞利散射原理,本文测量了空气电火花冲击波流注放电等离子体射流的时变电子密度.实验结果表明:测量系统的标定参数A为1.04 × 105 V·Ω·m–2;空气流注放电等离子体射流的电子密度与等离子体射流的半径和长度有关,结合高速放电影像展示的等离子体射流的等效半径和等效长度,测定的电子密度在1020 m–3的量级,且随时间先快速增长至峰值再成指数衰减.此外,本文还探讨了等离子体射流的不同等效尺度对测定结果的影响;分析结果表明,采用时变等效半径和时变等效长度的计算结果最有效,且第1个快速波峰是由光电离的电离波导致的.     

3d过渡金属掺杂M_2@Si_(20)(M=Sc-Zn)团簇的密度泛函理论研究

利用密度泛函理论(DFT)研究3d过渡金属掺杂硅团簇的几何结构和稳定性,计算了绝热电子亲和能和垂直电离能,内嵌双金属间距,自旋磁矩等.结果表明内嵌的Sc、Ti、V、Mn金属二聚体和十二面体硅笼构成了稳定的富勒烯结构,随着d电子数目的增加其内嵌的富勒烯构型有部分畸变,总体而言Si_(20)团簇掺杂双金属后稳定性得到了提高.     

A new study of associating inhomogeneous fluids with classical density functional theory

ABSTRACT

A new density functional for the study of associating inhomogeneous fluids based on Wertheim's first-order thermodynamic perturbation theory is presented and compared to the most currently used associating density functionals. This functional is developed using the weighted density approximation in the range of association of hard spheres. We implement this functional within the framework of classical density functional theory together with modified fundamental measure theory to account for volume exclusion of hard spheres. This approach is tested against molecular simulations from literature of pure associating hard spheres and mixtures of non-associationg and associating hard spheres with different number of bonding sites close to a hard uniform wall. Furthermore, we compare and review our results with the performance of associating functionals from literature, one based on fundamental measure theory and the inhomogeneous version of Wertheim's perturbation theory. Results obtained with classical DFT and the three functionals show excellent agreement with molecular simulations in systems with one hard wall. For the cases of small pores where only one or two layers of fluid are allowed discrepancies between results with classical DFT and molecular simulations were found.     

A giant enhancement of magnetic moment in a ternary three-shell icosahedral cluster: Fe@Mn12@Au20

ABSTRACT

The average magnetic moment per atom of Mn₁₃ cluster is expected to be enhanced by doping or coating with a shell. Several ternary core–shell icosahedral clusters TM@Mn₁₂@Au₂₀ were constructed by combining substituting the central Mn with VIII elements (Fe, Co, Ni, Ru, Rh, Pd and Pt) and coating with a icosahedral Au₂₀ shell, and systematically studied by using the first-principles density functional method. Compared to Mn₁₃, Fe@Mn₁₂@Au₂₀ cluster shows a giant enhancement on total magnetic moment (52?µ_B) which can be greatly attributed to the ferromagnetic coupling between spin moments of atoms. Coating with Au₂₀ shell enlarged the average distances of TM-Mn and Mn-Mn and is a useful way to change the magnetic coupling style. By analysis of density of states and electron localisation functional, we can conclude that the weak hybridisation between Fe and Mn in Fe@Mn₁₂@Au₂₀ is propitious to maintain their original direction of spin moments of atoms and then form ferromagnetic coupling.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

Nb(iPrNPMe2)3Fe–PMe3: A potential high reactivity heterobimetallic catalyst for acetylene cycloadditions

Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(ⁱPrNPMe₂)₃Fe–PMe₃, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(ⁱPrNPMe₂)₃Fe–PMe₃ can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(ⁱPrNPMe₂)₃Fe–PMe₃ to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(ⁱPrNPMe₂)₃Fe–PMe₃ is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(ⁱPrNPMe₂)₃Fe–PMe₃ moves from niobium to iron.     

Gold-Catalyzed Cross-Coupling Reactions: An Overview of Design Strategies,Mechanistic Studies,and Applications

Transition-metal-catalyzed cross-coupling reactions are central to many organic synthesis methodologies. Traditionally, Pd, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently, many studies have showed that both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions. Here, an overview of the past studies, current trends, and future directions in the field of gold-catalyzed coupling reactions is presented. Design strategies to accomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and experimental mechanistic studies, and their applications in diverse fields are critically reviewed. Specific topics covered are: oxidant-assisted and oxidant-free reactions; strain-assisted reactions; dual Au and photoredox catalysis; bimetallic synergistic reactions; mechanisms of reductive elimination processes; enzyme-mimicking Au chemistry; cluster and surface reactions; and plasmonic catalysis. In the relevant sections, theoretical and computational studies of Au^I/Au^III chemistry are discussed and the predictions from the calculations are compared with the experimental observations to derive useful design strategies.