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

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)

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 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)

重症与轻症登革热 B 细胞反应动态变化及差异

【目的】探讨登革病毒I型（DENV-1）感染时，机体B细胞和浆细胞随病程的动态变化及其与疾病严重性的关系，为重症登革热的早期预警或治疗提供可能依据。【方法】选择2014年9月至12月登革热住院病例62例，设轻症登革热组（DF，n=33）、重症登革热组（SD，n=29）及对照组（control，n=6）。采用多色流式细胞技术分析患者急性期及极期的外周血中B细胞及浆细胞随病程的动态变化及其在重症和轻症组的差异。进一步通过系列样品分析同一感染者（包括轻症和重症各3例）浆细胞随病程的变化，并且观察登革病毒初次及二次感染时，B细胞及其亚群即初始B细胞、记忆B细胞和浆细胞的变化。【结果】重症组B细胞扩增明显高于轻症组（=0.013），特别是在病程第5~6天（=0.017，0.002）。轻症组和重症组浆细胞与对照组相比均有明显的增殖（=0.011，0.032），但轻症和重症两组间相比差异无统计学意义。同一感染者系列样品分析显示，轻症病例浆细胞在病程第7~8天达高峰，第10天基本恢复正常。重症病例在病程第7~9天达高峰，但在病程10d后仍有一定量的增殖。对于轻症登革热，二次感染组表现出更明显的B细胞增殖、初始B细胞减少及记忆B细胞减少（=0.028，0.010，0.037），但浆细胞变化未体现出差异。而对于重症登革热，在二次感染时仅初始B细胞明显减少（=0.018）。【结论】DENV-1血清型感染时轻症和重症登革热组B细胞反应呈现不同的趋势。宿主在病程早期B细胞的明显扩增以及浆细胞延迟反应可能与疾病严重性相关

动脉粥样硬化性肾动脉狭窄的早期发现

探讨冠状动脉造影同时行肾动脉造影的必要性及动脉粥样硬化性肾动脉狭窄的相关危险因素分析。共 4 91例临床疑似冠心病患者行冠状动脉造影同时行非选择性或选择性肾动脉造影 ,并对相关的临床因素进行评价 ,筛选出动脉粥样硬化性肾动脉狭窄的独立危险因素。冠心病组患者中动脉粥样硬化性肾动脉狭窄的发病率为2 0 % ,显著高于非冠心病组 (2 .6 % )。冠心病、外周血管疾病是动脉粥样硬化性肾动脉狭窄的独立危险因素 (多元Logistic回归分析示 ,P <0 .0 0 1、P =0 .0 0 3) ,是其早期发现的指标。对怀疑有冠心病的患者 ,在冠状动脉造影同时行肾动脉造影有助于动脉粥样硬化性肾动脉狭窄的早期发现

Research on the Mechanisms by Which Thermophilic Fungi Promote the Hyphal Growth of Agaricus bisporus

嗜热真菌是蘑菇堆肥二次发酵后培养阶段的主要微生物类群。它们在堆肥中的数量及活性与蘑菇的产量有很大的相关性。本文综述了近年来，国外以嗜热色串孢（SCyTAlIdIuMTHErMOPHIluM）为典型种，研究其对蘑菇菌丝促生作用的生物机制的主要成果，国外主要研究了嗜热色串孢在堆肥中的分布、数量，生长动力学特性以及呼吸机制等，同时发现嗜热色串孢的呼吸作用形成适宜的CO2浓度可使得蘑菇菌丝尽早占料，获取生态优势，本文还介绍了国内有关嗜热真菌的研究及应用。Thermophilic Fungi are the dominant species among all kinds of microorganisms in mush-room compost during the temperature-controlled process of phase Ⅱ.The amount and activity of the Fun-gal mycelium have been observed to be positively correlated with mushroom yield.This article summaries the recent research on the mechanisms by which thermophilic Fungi promote thehyphal growth of Agaricus bisporus.In order to study the growth-promoting eFFect by these Fungi, Scytal-idium thermophilum was used as a model organism to investigate its distribution and amount in compost,growth characteristics,respiration pathway.The results showed that the concentration of CO2 was an im-portant parameter that inFluenced the hyphal extension rates of Agaricus bisporus.The research in China was also presented

“营改增”后房地产企业的税收筹划

我国开展了税制改革的重头戏“营改增”,减少了企业重复征税,有利于建设对经济的发展更加有力的税收环境。自2012年1月1日起,我国在上海率先实行营业税改征增值税(以下简称“营改增”)试点。第十二届全国人大第四次工作会议上,国务院总理李克强指出,全面实施“营改增”,将试点范围扩大。房地产业是国家经济中重要组成部分,房地产业“营改增”后的税收筹划的变化将影响后续营改增试点的发展。</jats:p

温度对油页岩快速热解特性的影响

采用喷动载流床快速热解装置,研究桦甸大城子4层油页岩的低温快速热解特性.采用改变气速的方法使不同热解温度下气体的停留时间一致,探讨不同热解温度对油页岩热解的气、液、固三相产物的产率、组成以及三者之间相互关系的影响,确定了在以获得液体燃料为主要目的时,530℃为桦甸大城子4层油页岩低温快速热解的最适宜温度