[目的]利用本课题组发展的定量分析方法研究激发态DNA碱基对分子间相互作用的本质,以及不同类型的电子跃迁对DNA碱基对分子间相互作用的影响.[方法]采用广义Kohn-Sham能量分解分析方法(generalized Kohn-Sham based energy decompositio...[目的]利用本课题组发展的定量分析方法研究激发态DNA碱基对分子间相互作用的本质,以及不同类型的电子跃迁对DNA碱基对分子间相互作用的影响.[方法]采用广义Kohn-Sham能量分解分析方法(generalized Kohn-Sham based energy decomposition analysis,GKS-EDA),对两种Waston-Crick构型和两种stacked构型的DNA碱基对分子间相互作用本质进行理论研究.[结果]对于Waston-Crick构型的碱基对,n→π^(*)跃迁削弱了轨道极化作用但加强了电子相关作用,激发态分子间相互作用由电子相关作用主导,而π→π^(*)跃迁对分子间氢键影响较小;对于stacked构型的碱基对,π→π^(*)跃迁削弱了静电相互作用但增强了电子相关作用.[结论]Waston-Crick构型碱基对分子间相互作用本质受电子激发跃迁影响较大,而电子激发跃迁基本不改变stacked构型碱基对分子间相互作用本质.展开更多
The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance,abysmal conductivity,and the resultant low practical capacity.To address these issues,a clas...The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance,abysmal conductivity,and the resultant low practical capacity.To address these issues,a class of bipolar p-phenylenediimidazole-based small-molecule compounds are designed and fabricated.Theπ-conjugated backbone of these small molecules allows for electron delocalization on a big conjugation plane,endowing them with good conductivity and reaction reversibility.Furthermore,when the para-positions of phenylene are occupied by hydroxyl groups,as-formed intramolecular hydrogen bonds(N-H...O)between phenolic hydroxyl groups and the–NH groups of imidazole rings further enhance the structural planarity,resulting in higherπ-conjugation degree and better conductivity,and thus higher utilization of active sites and electrode capacity,proved by both experimental results and theoretical calculations.The optimized composite electrode DBNQ@rGO-45 shows a high specific capacity(∼308 mA h g^(−1)at 100 mA g^(−1))and a long cycling stability(112.9 mA h g^(−1)after 6000 cycles at 2000 mA g^(−1)).The significantly better electrochemical properties for hydroxyl group-containing compounds than those without hydroxyl groups attributed to intramolecular hydrogen bond-induced conjugation enhancement will inspire the structure design of organic electrodes for better energy storage.展开更多
The interfacial chemistry of solid electrolyte interphases(SEI)on lithium(Li)electrode is directly determined by the structural chemistry of the electric double layer(EDL)at the interface.Herein,a strategy for regulat...The interfacial chemistry of solid electrolyte interphases(SEI)on lithium(Li)electrode is directly determined by the structural chemistry of the electric double layer(EDL)at the interface.Herein,a strategy for regulating the structural chemistry of EDL via the introduction of intermolecular hydrogen bonds has been proposed(p-hydroxybenzoic acid(pHA)is selected as proof-of-concept).According to the molecular dynamics(MD)simulation and density functional theory(DFT)calculation results,the existence of hydrogen bonds realizes the anion structural rearrangement in the EDL,reduces the lowest unoccupied molecular orbital(LUMO)energy level of anions in the EDL,and the number of free solvent molecules,which promotes the formation of inorganic species-enriched SEI and eventually achieves the dendrite-free Li deposition.Based on this strategy,Li‖Cu cells can stably run over 185 cycles with an accumulated active Li loss of only 2.27 mAh cm^(-2),and the long-term cycle stability of Li‖Li cells is increased to 1200 h.In addition,the full cell pairing with the commercial LiFePO_(4)(LFP)cathodes exhibits stable cycling performance at 1C,with a capacity retention close to 90%after 200 cycles.展开更多
文摘[目的]利用本课题组发展的定量分析方法研究激发态DNA碱基对分子间相互作用的本质,以及不同类型的电子跃迁对DNA碱基对分子间相互作用的影响.[方法]采用广义Kohn-Sham能量分解分析方法(generalized Kohn-Sham based energy decomposition analysis,GKS-EDA),对两种Waston-Crick构型和两种stacked构型的DNA碱基对分子间相互作用本质进行理论研究.[结果]对于Waston-Crick构型的碱基对,n→π^(*)跃迁削弱了轨道极化作用但加强了电子相关作用,激发态分子间相互作用由电子相关作用主导,而π→π^(*)跃迁对分子间氢键影响较小;对于stacked构型的碱基对,π→π^(*)跃迁削弱了静电相互作用但增强了电子相关作用.[结论]Waston-Crick构型碱基对分子间相互作用本质受电子激发跃迁影响较大,而电子激发跃迁基本不改变stacked构型碱基对分子间相互作用本质.
基金the financial support by the National Natural Science Foundation of China (22371010, 21771017, and 51702009)the "Hundred Talents Program" of the Chinese Academy of Sciences, the Fundamental Research Funds for the Central Universities+1 种基金the Shenzhen Science and Technology Program (JCYJ20210324115412035, JCYJ2021-0324123202008, JCYJ20210 324122803009 and ZDSYS20210813095534001)the Guangdong Basic and Applied Basic Research Foundation (2021A1515110880)
文摘The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance,abysmal conductivity,and the resultant low practical capacity.To address these issues,a class of bipolar p-phenylenediimidazole-based small-molecule compounds are designed and fabricated.Theπ-conjugated backbone of these small molecules allows for electron delocalization on a big conjugation plane,endowing them with good conductivity and reaction reversibility.Furthermore,when the para-positions of phenylene are occupied by hydroxyl groups,as-formed intramolecular hydrogen bonds(N-H...O)between phenolic hydroxyl groups and the–NH groups of imidazole rings further enhance the structural planarity,resulting in higherπ-conjugation degree and better conductivity,and thus higher utilization of active sites and electrode capacity,proved by both experimental results and theoretical calculations.The optimized composite electrode DBNQ@rGO-45 shows a high specific capacity(∼308 mA h g^(−1)at 100 mA g^(−1))and a long cycling stability(112.9 mA h g^(−1)after 6000 cycles at 2000 mA g^(−1)).The significantly better electrochemical properties for hydroxyl group-containing compounds than those without hydroxyl groups attributed to intramolecular hydrogen bond-induced conjugation enhancement will inspire the structure design of organic electrodes for better energy storage.
基金financially supported by the National Natural Science Foundation of China(Grant No.21905033,52271201)the Key Research and DevelopmentProgram of Sichuan Province(Grant No.2022YFG0100)+1 种基金the Central Government Funds of Guiding Local Scientific and Technological Development for Sichuan Province(Grant No.2022ZYD0045)the State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization(Grant No.2020P4FZG02A)
文摘The interfacial chemistry of solid electrolyte interphases(SEI)on lithium(Li)electrode is directly determined by the structural chemistry of the electric double layer(EDL)at the interface.Herein,a strategy for regulating the structural chemistry of EDL via the introduction of intermolecular hydrogen bonds has been proposed(p-hydroxybenzoic acid(pHA)is selected as proof-of-concept).According to the molecular dynamics(MD)simulation and density functional theory(DFT)calculation results,the existence of hydrogen bonds realizes the anion structural rearrangement in the EDL,reduces the lowest unoccupied molecular orbital(LUMO)energy level of anions in the EDL,and the number of free solvent molecules,which promotes the formation of inorganic species-enriched SEI and eventually achieves the dendrite-free Li deposition.Based on this strategy,Li‖Cu cells can stably run over 185 cycles with an accumulated active Li loss of only 2.27 mAh cm^(-2),and the long-term cycle stability of Li‖Li cells is increased to 1200 h.In addition,the full cell pairing with the commercial LiFePO_(4)(LFP)cathodes exhibits stable cycling performance at 1C,with a capacity retention close to 90%after 200 cycles.
