Photoinduced intramolecular charge separation in donor/acceptor-substituted bicyclohexylidene and bicyclohexyl

The photophysical properties of a bicyclohexylidene (1DA) and a bicyclohexyl (2DA) substituted with an anilino electron donor and a dicyanoethylene electron acceptor have been studied. Quenching of local donor emission is observed for these compounds as well as quenching of the "pseudo-local" acceptor emission. Transient absorption spectra show dialkylanilino-type radical-cation and dicyanoethylene-type radical-anion absorptions. These results show that intramolecular charge separation takes place in 1DA and 2DA. This was corroborated by time-resolved microwave conductivity measurements from which large excited-state dipole moments were found for both 1DA and 2DA. Time-resolved fluorescence spectroscopy revealed that in the charge-separated state in cyclohexane for 2DA, molecular folding takes place on a nanosecond timescale. For 1DA in cyclohexane, either charge separation takes place in a (fully) folded conformation or very rapid (subnanosecond timescale) folding takes place subsequent to charge separation. In addition to this difference in conformational behavior, the presence of the exocyclic double bond between the cyclohexyl-type rings results in efficient quenching of the anilino donor triplet state and acceleration of the charge recombination rate by a factor of 20.     

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions

Acetonitrile (CH₃CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C?H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C?H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH₃ to CN along the CH???N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp² and sp³ bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C?H can be activated by high pressure, even at room temperature and without a catalyst.     

Pressure-Induced Polymerization of Acetylene: Structure-Directed Stereoselectivity and a Possible Route to Graphane

Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Following this route produces a pure cis-isomer and more surprisingly, predicts that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure.     

Design of polarization-maintaining retro-reflector for folded-path applications

A design of polarization-maintaining retro-reflectors(PMRRs) for folded-path applications is proposed and analyzed.The prism-based scheme enables the output light,which is parallel to the input,to have an identical state of polarization.The principle of the design is theoretically verified,and the related error is analyzed due to possible manufacturing imperfection.The maximum spatial angle error is ±2.75°.The effect on the extinction ratio and insertion loss is also discussed,which further proves the design’s feasibility in practical applications.     

关于n+k相多体系(k≥4)封闭网的构造

本文证明了n+k多体系(k≥4)的全部可能的封闭网均可以通过若干相应的子n+3相多体系的拼合运算得出,从而为具体构造n+k相多体系(k≥4)的全部合理的封闭网,提供了基本方法。     

超导临界温度理论(Ⅱ)

在文献[1]中,我们导出了超导临界温度T-c的一个严格级数表式.本文讨论这个级数的收敛范围,以及通过解析延拓来扩展收敛范围的可能性.结论是:我们的T_c级数(指文献[1]原来的级数,或者经过延拓后的级数)在∞>λ>λ₀的整个范围内,都是收敛的.这里λ₀是Matsubara表象中使决定T_c的方程具有正实数解的最小的λ值.它实际上就是库伦赝势.因此,也许除了少数非常弱耦合的超导体以外,我们的T_c级数能适用于一切超导体.     

裂缝的张开位移和应变的关系

本文采用Kármán-钱处理亚音速流动方法的精神。处理了弹塑性断裂力学问题.通过建立的“双弹性”模型,从理论上得到了裂缝端部的张开位移和应变的方程组.实例计算结果表明,理论值全部落在实验结果的分散带内.文中并从理论上解释了实验结果与材料的性质及实验条件的关系.本文的结果不仅为宽板实验所证实,也被文献[2]的实验所证实.同时也表明。公式(37)用于工程,能够分析压力容器上应变裂缝的容许极限.     

低温等离子体转化NO/O2/N2气氛中NO的实验研究

通过建立低温等离子体实验系统, 研究了介质阻挡放电型低温等离子体反应器作用于NO/O2/N2混合气体系时, NO, O2初始浓度对NO的转化效率的影响以及NOx, O3浓度随能量密度的变化关系. 低温等离子体作用于NO/O2/N2混合气体系时, NO同时发生氧化还原反应, 氧化反应占主导地位, 大部分NO转化为NO2; NO转化率随O2, NO初始浓度增大而降低, 能量密度在450～600 J/L时转化率较高; 产生的O3浓度随能量密度的增大呈先增后减的趋势.     

Astrophysical S-factors from asymptotic normalization coefficients

S-factors for direct capture reactions can be found at astrophysical energies from asymptotic normalization coefficients which provide the normalization of the tail of the overlap function. For example the overlap for ⁸B → ⁷Be+p defines the S-factor for ⁷Be (p, γ)⁸B. Peripheral transfer reactions offer a technique to determine these asymptotic normalization coefficients. As a test of the technique, the ¹⁶O(³He, d)¹⁷F reaction has been used to determine asymptotic normalization coefficients for transitions to the ground and first excited states of ¹⁷F. The S-factors for ¹⁶O(p, γ)¹⁷F calculated from these ¹⁷F → ¹⁶O+p asymptotic normalization coefficients are found to be in very good agreement with recent measurements. Following the same technique, the ¹⁰B(⁷Be, ⁸B)⁹Be and ¹⁴N(⁷Be, ⁸B)¹³C reactions have been used to measure the asymptotic normalization coefficient for ⁷Be(p, γ)⁸B. This result provides an indirect determination of S ₁₇(0).