利用扫描隧道显微术、扫描隧道谱和密度泛函理论研究了茚并[1,2-b]芴-6,12-二酮(IFDO)在Au(111)表面形成的组装结构及其中分子轨道能级的变化.结果表明, IFDO在Au(111)表面通过分子间氢键沿鱼骨重构结构形成一维自组装分子链;位于组装...利用扫描隧道显微术、扫描隧道谱和密度泛函理论研究了茚并[1,2-b]芴-6,12-二酮(IFDO)在Au(111)表面形成的组装结构及其中分子轨道能级的变化.结果表明, IFDO在Au(111)表面通过分子间氢键沿鱼骨重构结构形成一维自组装分子链;位于组装结构中的分子的最低未占轨道相对孤立分子向费米能级方向发生0.16~0.32 e V的位移,且位移大小与分子同周围分子形成氢键的数目和方式有关.通过定量地对比不同氢键环境中分子的轨道能量位移与周围分子极化能大小的变化趋势,发现周围分子的瞬时极性是造成组装结构中IFDO分子轨道能量变化的主要因素.而周围分子的诱导极性则对缺陷结构处分子的轨道能级有不可忽略的影响.实验测得的IFDO分子轨道的能量变化来自于周围分子各向异性的瞬时极性和诱导极性的共同作用.展开更多
Based on the construction bridge of Xiamen-Shenzhen high-speed railway(9-32 m simply-supported beam + 6×32 m continuous beam),the pier-beam-track finite element model,where the continuous beam of the ballast trac...Based on the construction bridge of Xiamen-Shenzhen high-speed railway(9-32 m simply-supported beam + 6×32 m continuous beam),the pier-beam-track finite element model,where the continuous beam of the ballast track and simply-supported beam are combined with each other,was established.The laws of the track stress,the pier longitudinal stress and the beam-track relative displacement were analyzed.The results show that reducing the longitudinal resistance can effectively reduce the track stress and the pier stress of the continuous beam,and increase the beam-track relative displacement.Increasing the rigid pier stiffness of continuous beam can reduce the track braking stress,increase the pier longitudinal stress and reduce the beam-track relative displacement,Increasing the rigid pier stiffness of simply-supported beam can reduce the track braking stress,the rigid pier longitudinal stress and the beam-track relative displacement.展开更多
2,4-diphenylpentane- and 2,4-di-p-tolylpentane-2,4-diols were investigated employing experimental and density functional theory （DFT） method at B3LYP/6-31G （d） level. The structure of syn-2,4-di-p-tolylpentane-2,4...2,4-diphenylpentane- and 2,4-di-p-tolylpentane-2,4-diols were investigated employing experimental and density functional theory （DFT） method at B3LYP/6-31G （d） level. The structure of syn-2,4-di-p-tolylpentane-2,4-diol （2b） was characterized by X-ray diffraction and compared with the crystal structures of anti- and syn-2,4-diphenylpentane-2,4-diols （la and lb）. X-ray diffraction indicates that inter and intra-molecular hydrogen bonds are formed in the crystal structures. There is n-n staking interaction in lb and 2b. Good linear correlations and similar results are found between the experimental 1H and 13C NMR chemical shifts （6~exp） and GIAO （Gauge Independent Atomic Orbital） method calculated magnetic isotropic shielding tensors （acalc）. HOMO and LUMO molecular orbitals were calculated at the same levels with the different results. UV-vis absorption spectra of the compounds were recorded in EtOH, MeCN, n-BuOH and cyclohexane with different dielectric constants. It is found that the solvent effect is obvious when e is 24.85（EtOH）, 35.69（MeCN） and it is weak when e is decreased to 17.33（n-BuOH）, 1.18 （cyclohexane）.展开更多
文摘利用扫描隧道显微术、扫描隧道谱和密度泛函理论研究了茚并[1,2-b]芴-6,12-二酮(IFDO)在Au(111)表面形成的组装结构及其中分子轨道能级的变化.结果表明, IFDO在Au(111)表面通过分子间氢键沿鱼骨重构结构形成一维自组装分子链;位于组装结构中的分子的最低未占轨道相对孤立分子向费米能级方向发生0.16~0.32 e V的位移,且位移大小与分子同周围分子形成氢键的数目和方式有关.通过定量地对比不同氢键环境中分子的轨道能量位移与周围分子极化能大小的变化趋势,发现周围分子的瞬时极性是造成组装结构中IFDO分子轨道能量变化的主要因素.而周围分子的诱导极性则对缺陷结构处分子的轨道能级有不可忽略的影响.实验测得的IFDO分子轨道的能量变化来自于周围分子各向异性的瞬时极性和诱导极性的共同作用.
基金Project(50678176) supported by the National Natural Science Foundation of China
文摘Based on the construction bridge of Xiamen-Shenzhen high-speed railway(9-32 m simply-supported beam + 6×32 m continuous beam),the pier-beam-track finite element model,where the continuous beam of the ballast track and simply-supported beam are combined with each other,was established.The laws of the track stress,the pier longitudinal stress and the beam-track relative displacement were analyzed.The results show that reducing the longitudinal resistance can effectively reduce the track stress and the pier stress of the continuous beam,and increase the beam-track relative displacement.Increasing the rigid pier stiffness of continuous beam can reduce the track braking stress,increase the pier longitudinal stress and reduce the beam-track relative displacement,Increasing the rigid pier stiffness of simply-supported beam can reduce the track braking stress,the rigid pier longitudinal stress and the beam-track relative displacement.
基金Projects(21072053,20772028)supported by the National Natural Science Foundation of ChinaProjects(10K025,11C0527)supported by the Scientific Research Fund of Hunan Provincial Education Department,ChinaProject(LKF0901)supported by the Open Foundation of Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education,Hunan University of Science and Technology,China
文摘2,4-diphenylpentane- and 2,4-di-p-tolylpentane-2,4-diols were investigated employing experimental and density functional theory （DFT） method at B3LYP/6-31G （d） level. The structure of syn-2,4-di-p-tolylpentane-2,4-diol （2b） was characterized by X-ray diffraction and compared with the crystal structures of anti- and syn-2,4-diphenylpentane-2,4-diols （la and lb）. X-ray diffraction indicates that inter and intra-molecular hydrogen bonds are formed in the crystal structures. There is n-n staking interaction in lb and 2b. Good linear correlations and similar results are found between the experimental 1H and 13C NMR chemical shifts （6~exp） and GIAO （Gauge Independent Atomic Orbital） method calculated magnetic isotropic shielding tensors （acalc）. HOMO and LUMO molecular orbitals were calculated at the same levels with the different results. UV-vis absorption spectra of the compounds were recorded in EtOH, MeCN, n-BuOH and cyclohexane with different dielectric constants. It is found that the solvent effect is obvious when e is 24.85（EtOH）, 35.69（MeCN） and it is weak when e is decreased to 17.33（n-BuOH）, 1.18 （cyclohexane）.
