Theoretical Study on the Electronic Spectra of cis-HOOOH and trans-HOOOH

用密度泛函方法(DFT)和全活化空间自洽场方法(CASSCF)以及耦合簇理论(CCSD)优化了反式和顺式HOOOH的平衡几何构型,用DFT计算了HOOOH顺反异构化反应的势能曲线和谐振动频率.用含时密度泛函理论(TD-DFT)和二阶全活化空间微扰理论(CASPT2)计算了反式和顺式HOOOH垂直激发能.计算结果表明:(1)反式异构体比顺式异构体稳定;(2)两种稳定构型的异构化反应有两种路径;(3)对于垂直跃迁能最低的单态和叁态,反式的垂直跃迁能比顺式的低;(4)在单激发态中,CASPT2方法预测的顺式HOOOH寿命最长的激发态为21A″,其跃迁能是167.43nm,寿命为1.44×10-5s;反式HOOOH寿命最长的激发态为21A,其跃迁能是165.52nm,寿命为2.07×10-5s.Equilibrium geometries of cis-HOOOH and trans-HOOOH have been investigated using the density functional theory (DFT), complete active space self-consistent-field (CASSCF), and coupled cluster with single and double replacement (CCSD) approaches. The harmonic vibrational frequencies on the optimized geometries were calculated using the DFT theory. The potential energy curve of the isomerization between the trans-HOOOH and cis-HOOOH was obtained by DFT calculations. Time-dependent density functional theory (TD-DFT) and complete active space perturbation theory of second order (CASPT2) calculations have been performed to obtain the vertical excitation energies of selected low-lying singlet and triplet excited states. Computed results show that: (1) trans-isomer is more stable than cis-isomer; (2) there are two pathways of the conversion between the trans-HOOOH and cis-HOOOH; (3) the vertical excitation energies of the lowest singlet and triplet excited states in trans-HOOOH are lower than those in cis-isomer; (4) in the singlet excited states, 21A state in trans-HOOOH and 21A″ state in cis-HOOOH have the longest lifetimes of 2.07×10-5 s and 1.44×10-5 s with the excitation energies of 165.52 and 167.43 nm, respectively.国家自然科学基金(20473062,20233020,20021002,20173042);; 厦门大学固体表面物理化学国家重点实验室开放课题基金(200306);; 河南省自然科学基金(0311011200,200510475012)资助项

Theoretical Study on Structures and Electronic Spectra of Linear Chain Cluster BC_(2n)B (n=1～12)

应用密度泛函理论,在B3LYP/6-31G*水平上优化得到了线性簇合物BC2B(n=1～12,D∞h)的平衡几何构型,并n计算了它们的谐振动频率.在优化平衡几何构型下,通过TD-B3LYP/cc-pvDZ和TD-B3LYP/cc-pvTZ计算,分别得到了n=1～12和n=1～7的X1Σg→11Σ+u电子跃迁的垂直激发能和对应的振子强度.在B3LYP/6-311+G*水平上计算得到+了簇合物BC2B(n=1～12,D∞h)的电离能.基于计算结果,导出了BC2B体系X1Σg→11Σ+u电子跃迁能以及第一电离能+nn与体系大小n的解析表达式.Using density functional theory, the geometries and the vibrational frequencies of linear chain BC2 B (n=1～12, D∞h) have been investigated at the B3LYP/6-31G* level. Time-dependent density func- n tional theory (TD-DFT) has been used to calculate the vertical transition energies and oscillator strengths for X1Σg →11Σ+u transitions of BC2 B with the cc-pvTZ and cc-pvDZ basis sets. At the B3LYP/6-311+G* + n level, the single-point energies of the clusters have been calculated in order to determine the first ionization energies. On the basis of present calculations, the explicit expressions for the size dependence of the excita- tion energy, the first adiabatic ionization energies (AIE) and vertical ionization energies (VIE) in linear car- bon chains were suggested.厦门大学固体表面物理化学国家重点实验室开放课题基金;; 国家自然科学基金;; 河南省自然科学基金(Nos. 20173042; 20233020; 20021002;0311011200)资助项目

Structure and Electronic Spectrum of Linear Carbon Chains LiC_(2n)Li Studied with Density Functional Theory

应用密度泛函理论,在B3LYP/6 31G(d)水平上优化得到了线型簇合物LiC2nLi(n=1 ~10,D∞h)的基态平衡几何构型,并计算了它们的谐振动频率.利用含时密度泛函理论,计算了簇合物LiC2nLi的X1∑ +g→11∑ +u跃迁的垂直激发能,以及相应的振子强度.基于计算结果,建立了跃迁能和体系大小n的解析关系式. 同时也计算了体系的第一绝热电离能,讨论了体系的电离能与体系大小n的关系.The geometries and the vibrational frequencies of linear chains LiC_(2n)Li(n=1~10) were investigated by density functional theory at the B3LYP/631G(d) level. Time-dependent density functional theory was used to calculate the vertical transition energies and oscillator strengths of X~1∑~+_g→1~1∑~+_u transitions in LiC_(2n)Li. Based on the present calculations, the explicit analytic expression between the vertical transition energies and n was obtained. Meanwhile, the first adiabaticionization energies werecalculated, and the relationship between the adiabaticionization energiesand nhas also been discussed.固体表面物理化学国家重点实验室(厦门大学)开放课题基金 (200306);; 国家自然科学基金 (20173042);; 河南省自然科学基金 资助项目(0311011200)

Structure and Electronic Spectrum of Linear Carbon Chain PC_(2n)P Studied with DFT

应用密度泛函理论,在B3LYP/6-31G**和B3LYP/6-311G**水平上优化得到了线型簇合物PC2nP(n=1-10)的基态平衡几何构型,计算了它们的谐振动频率.在基态平衡构型下,利用含时密度泛函理论,计算得到了簇合物PC2nP(n=1-10)的垂直激发能和相应的振子强度,导出了激发能与体系大小n的解析关系式.The geometries and the vibrational frequencies of linear carbon chain PC_ 2nP (n=1-10) were investigated by density functional theory(DFT) at the B3LYP/6-31G ** and B3LYP/6-311G ** levels. Time-dependent density functional theory (TD-DFT) was employed to calculate the vertical transition energies and oscillator strengths. On the basis of present calculations, the explicit expressions for the size dependence of the excitation energy in linear carbon chain was suggested.ThisresearchwassupportedbyStateKeyLaboratoryforPhysicalChemistryofSolidSurfaces(XiamenUniversity)(200306),andNaturalScienceFoundationofChina(20173042,20233020)

三重疗法治疗雄激素性脱发疗效分析

目的:通过三重疗法治疗雄激素性脱发,并进行疗效分析。方法:66例雄激素性脱发病人随机分为试验组与针刺组,每组各33例。试验组采取针刺、梅花针联合实按灸疗法,针刺组采取针刺疗法。记录两组患者的疗效及伴随症状评分情况。结果:试验组的总有效率为81. 82%,针刺组的总有效率为57. 58%。两组的疗效比较差异具有统计学意义(P <0. 05)。治疗后,试验组的伴随症状评分均低于针刺组,差异均具有统计学意义(P <0. 05)。结论:电针、梅花针联合实按灸疗法治疗雄激素性脱发疗效显著,临床上具有推广及应用价值。中国中医科学院“十三五”重点领域研究专项第一批(No.ZZ10-011-1-2

a quick network constructing method based on adaptive grouping

针对现有的网络环境构建方法部署效率低和灵活性差的缺点,提出一种基于分组自适应策略的网络环境快速构建方法.根据软件部署时间的分布特点采取适当的分组方法,减少主机共有软件的重复部署时间,提高软件部署效率.在此基础上,实现了一套以分组自适应策略为基础的网络环境快速构建原型系统.对提出的相关策略和算法进行了验证.Direct deployment and computer cloning are the two existing network constructing methods,which have low efficiency and flexibility.We propose a quick network constructing method using adaptive grouping policy based on the distribution characteristics of deployment time.The method reduces repeated deployment time and improves efficiency.An adaptive grouping-based quick network constructing prototype system is implemented and the algorithm is verified

Electronic Absorption Spectra of Linear Cluster SC_(2n)S~(2-)(n=1～12)

应用密度泛函理论,在B3LYP/6-31G水平上优化了线性簇合物SC2nS2-(n=1～12)的基态平衡几何结构,并计算了它们的谐振动频率.在基态平衡构型下,通过TD-B3LYP/cc-pvTZ和TD-B3LYP/cc-pvDZ计算,确定了簇合物SC2nS2-(n=1～10)X1Σ+g→11Σ+u电子跃迁的垂直激发能和对应的振子强度.基于计算结果,导出了X1Σ+g→11Σ+u电子跃迁吸收波长与体系大小n的解析关系式,以及SC2nS2-体系第一电离能与体系大小n的解析表达式,并讨论了不同端位原子对碳链体系激发态性质的影响.Using density functional theory(DFT),the geometries and the vibrational frequencies of linear cluster SC2nS2-(n=1～12) have been investigated at the B3LYP/6 31Glevel.Time dependent density functional theory(TD DFT) has been used to calculate the vertical transition energies and oscillator strengths for transitions of SC2nS2-at the B3LYP/cc pvTZ and B3LYP/cc pvDZ levels.On the basis of theoretical results,an explicit expression for the size dependence of the excitation energy in linear carbon chains is obtained.Present calculations show that the terminal sulfur atom may significantly effect the excited state properties of the conjugated carbon chains.At the B3LYP/ 6 311+Glevel,the single point energies of the ionic clusters have been calculated in order to determine the first ionization energies.The relationship between the cluster size and the first ionization energies of the linear carbon chains is proposed.固体表面物理化学国家重点实验室(厦门大学)开放课题基金;; 河南省自然科学基金;; 国家自然科学基金(20173042;20233020;20021002)资助项目~

Molecular mechanism and carbon sink effects of microbial transformation in potassium- bearing rocks

Microbial mineral weathering is one of the most active and universal geological processes in the earth surface system.Microorganisms can degrade potassium-bearing rocks (mainly silicate minerals), release elements such as potassium,silicon and calcium,and promote mineral carbonate precipitation under appropriate environmental conditions,functioning as an important link in the geochemical cycles of earth surface elements.Microbial biotransformation of rocks involves growths and metabolic regulations of microorganisms,migration and transformation of elements and evolutionary sequence of secondary mineralsall are important research topics in mineralogy,microbiology and molecular biology.Combining researches in these areas is beneficial for systematically studying the process of microbial weathering of potassiumcontaining silicate minerals coupled with carbonation and its molecular regulation mechanism.It was confirmed that under the conditions of pure culture experiments,the synergistic effects of acidolysis, chelation,oxidoreduction and other chemical activities are effective in the microbial weathering processes, and the effective weathering can also be achieved by regulating the microbial relevant functional gene expression in response to potassium-deficient environments.Such effects clearly depend on a refined and specific molecular regulation mechanism through long-term evolution of microorganisms.In the soil ecological environment,a significant feature of microbial mineral weathering is the cooperative interaction of microbial communities in the habitats.The participation of microbial carbonic anhydrase in silicate mineral weathering,along with carbonate mineral formation,may be a long-neglected process of earth surface carbon sink.An in-depth exploration of such process will help us further understand the mechanisms of microbial driving carbon migration and transformation in geologic evolutionary history.The utilization of organic fertilizers containing potassium-bearing rock powders has shown positive effects on soil improvement, crop growth and carbon sequestration,which provides a new idea for using the biological weathering of silicate minerals to delay the continuous increase of atmospheric CO_2 concentration.In this paper,we reviewed the molecular mechanisms and carbon sequestration effect of potassium released from biotransformation of potassium-bearing rocks by microorganisms,so as to promote rapid development in this research area

含钾岩石微生物转化的分子机制及其碳汇效应

岩石矿物的微生物风化是地球表层系统最为活跃和普遍发生的地质营力之一。微生物对含钾岩石(以硅酸盐矿物为主)的风化能够释放其中的钾、硅和钙等元素,并在合适的环境条件下促进矿物元素的碳酸化沉淀,这是地表元素地球化学循环的重要环节之一。微生物对岩石的生物转化作用既涉及微生物的生长繁殖和代谢调控,也与元素的迁移转化和次生矿物的演化序列有关,具有重要研究价值。采用矿物学、微生物学和分子生物学等相结合的研究方法,有助于系统地研究微生物促进含钾硅酸盐矿物的风化并耦联碳酸化过程及其分子调控机制。研究证实,在纯培养条件下,微生物风化含钾矿物主要采用酸解、螯合、氧化还原等多种方式的协同作用,并可通过调控相关功能基因的表达来响应缺钾的环境以实现其对含钾矿物的有效风化,显然这有赖于微生物通过长期进化而形成的精细的分子调控机制。在土壤生态环境中,微生物对矿物风化的显著特征是该生态环境中微生物群落协同互作的群体作用效应。微生物碳酸酐酶参与的硅酸盐矿物风化伴随碳酸盐矿物的形成过程可能是个长期被忽视的地表碳增汇过程,对该问题的深入探索有助于进一步理解地质演化历史中微生物对碳素迁移转化的驱动机制。加入含钾硅酸盐矿粉的有机肥已经显示出其在土壤改良、作物生长和增加土壤碳汇等方面的正面应用效果,这为利用硅酸盐矿物的生物风化作用来延缓大气CO_2浓度的持续升高提供了新的思路。介绍了有关微生物对含钾岩石生物转化释放钾素的分子机理及其碳汇效应方面的研究进展,以期抛砖引玉,推动该领域研究的快速发展

Theoretical study on structures and electronic spectra of linear chain cluster BC2nB (n=1 similar to 12)

Using density functional theory, the geometries and the vibrational frequencies of linear chain BC2nB (n=1similar to12, D-infinityh) have been investigated at the B3LYP/6-31G(*) level. Time-dependent density functional theory (TD-DFT) has been used to calculate the vertical transition energies and oscillator strengths for X(1)Sigma(g)(+)-->1(1)Sigma(u)(+) transitions of BC2nB with the cc-pvTZ and cc-pvDZ basis sets. At the B3LYP/6-311+G(*) level, the single-point energies of the clusters have been calculated in order to determine the first ionization energies. On the basis of present calculations, the explicit expressions for the size dependence of the excitation energy, the first adiabatic ionization energies (AIE) and vertical ionization energies (VIE) in linear carbon chains were suggested