A flexible correlation group table (CGT) method for the relativistic configuration interaction wavefunctions

A generalized correlation group table (CGT) method is described for the relativistic configuration interaction (RCI) wavefunctions of molecules containing heavy atoms. In this method first four keywords are defined and two properties are discussed in terms of spectroscopic states and double group theory. These definitions and properties are then used to summarize six principles to stipulate the relationship among relativistic states, nonrelativistic states, as well as RCI configurations. The definitions, properties, and principles comprise the generalized CGT method, which facilitates the classification and assignment of the RCI wavefunctions, and thus, provide a general technique for complex systems containing several open shells. Finally, the techniques are exemplified with a few computational models.     

确定金属酶及模拟络合物中金属离子氧化态的一种方法——键价和分析

在生物化学领域中弄清金属酶活性中心的结构和氧化态是至关重要的。“键价和分析”是根据金属 配体键长数据确定固体中金属离子氧化态的一种方便可行的方法 ,它已用于金属蛋白、金属酶以及高温超导体中金属氧化态的指派。本文拟介绍该方法的要点及其实际应用。     

A flame retardant separator modified by MOFs-derived hybrid for safe and efficient Li-S batteries

In this work,we have successfully prepared a novel separator modified with N,S co-doped carbon framework(named NSPCF)with confined CoS₂ nanoparticles and rooted carbon nanotubes material(named NSPCF@CoS₂)to apply for high-performance Lithium-Sulfur batteries(Li-S batteries).Robust carbon structure with large specific surface can act as a physical barrier and possess physical adsorption effect on lithium polysulfides(LiPSs).In addition,highly-conductive carbon can improve integral conductivity,leading to the fast charge transport and reaction kinetics.Also,doping heteroatoms could form more active sites to adsorb LiPSs strongly so that modified separator could inhibit the shuttle effect effectively.Moreover,the presence of CoS₂ further enhances the ability of modified separator to trap LiPSs owing to the Lewis acid-base action.As a result,the NSPCF@CoS₂@C-150 battery can deliver initial discharge capacities of 863.0,776.2,649.1 and 489.4 mAh g^-1 at 0.1,0.5,1 and 2C with a high sulfur loading of 2.04 mg cm^-2,respectively.Notably,when turning the current density back to 0.1 C,its discharge capacity can recover to 1008.7 mAh g^-1.In addition,the modified separators exhibit outstanding capacities to restrain the growth of lithium dendrites.It is noteworthy that the flame retardant performances of Li-S batteries are improved dramatically owing to the novel structures of modified separators.This rationally designed separator endows Li-S batteries with higher safety and excellent electrochemical performances,providing a feasible strategy for practical application of Li-S batteries.     

Three-body entanglement induced by spontaneous emission in a three two-level atoms system

We study three-body entanglement induced by spontaneous emission in a three two-level atoms system by using the entanglement tensor approach. The results show that the amount of entanglement is strongly dependent on the initial state of the system and the species of atoms. The three-body entanglement is the result of the coherent superposition of the two-body entanglements. The larger the two-body entanglement is, the stronger the three-body entanglement is. On the other hand, if there exists a great difference in three two-body entanglement measures, the three-body entanglement is very weak. We also find that the maximum of the two-body entanglement obtained with nonidentical atoms is greater than that obtained with identical atoms via adjusting the difference in atomic frequency.     

Synthesis of 4‐(5‐aryl‐1,3,4‐oxadiazol‐2‐yl)phenyl‐hydrazine derivatives from 3‐(4‐hydrazinocarbonyl‐phenyl)sydnones

The synthesis of potential fluorescent active 4‐(5‐aryl‐1,3,4‐oxadiazol‐2‐yl)phenylhydrazine derivatives was accomplished in three steps. The key step was the dehydration cyclization of 1,2‐diacylhydrazines to form the 1,3,4‐oxadiazole ring by use of acetic anhydride/perchloric acid mixture as the dehydrating agent. The sydnone moiety served as the masked hydrazines, which could be demasked by HCl for further application. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:438–442, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20318     

Synthesis,Crystal Structure and Spectral Properties of [Fe<Subscript>3</Subscript>(2,2′-bipy)<Subscript>6</Subscript>(ox)<Subscript>3</Subscript>]·12.25H<Subscript>2</Subscript>O Complex

A novel iron (II) complex of formula [Fe₃(2,2′-bipy)₆(ox)₃]·12.25H₂O (2,2′-bipy = 2,2′-bipyridine, ox = oxalate) has been prepared and structurally characterized by X-ray crystallography. In the complex, the metal atoms are six-coordinated in distorted octahedral environment. In the complex [Fe(ox)₃]^4? anions and water molecules are linked together into 1D chain structure by hydrogen interaction. The red crystal of the complex is monoclinic, space group P2₁/c, with a = 22.932(6) Å, b = 13.715(4) Å, c = 22.493(6) Å, β = 93.177(5)°, and V = 7063(3) Å³ with Z = 4.     

正碳离子样的过渡态类似物研究进展

综述了应用酶催化过渡态理论设计的几类正碳离子样的过渡态类似物作为酶的抑制剂的研究进展。其中包括类异戊二烯的正离子过渡态类似物,唾液酸转移酶的过渡态类似物,3-脱氧-D-甘露糖-2-辛酮糖酸酯-8-磷酸酯(KDO8P) 合成酶的过渡态类似物,尿苷二磷酸酯葡糖醛酸基转移酶(UGT) 的过渡态类似物。     

Theoretically probing the possible degradation mechanisms of an FeNC catalyst during the oxygen reduction reaction

For the FeNC catalyst widely used in the oxygen reduction reaction (ORR), its instability under fuel cell (FC) operating conditions has become the biggest obstacle during its practical application. The complexity of the degradation process of the FeNC catalyst in FCs poses a huge challenge when it comes to revealing the underlying degradation mechanism that directly leads to the decay in ORR activity. Herein, using density functional theory (DFT) and ab initio molecular dynamics (AIMD) approaches and the FeN₄ moiety as an active site, we find that during catalyzing the ORR, Fe site oxidation in the form of *Fe(OH)₂, in which 2OH* species are adsorbed on Fe on the same side of the FeN₄ plane, results in the successive protonation of N and then permanent damage to the FeN₄ moiety, which causes the leaching of the Fe site in the form of Fe(OH)₂ species and a sharp irreversible decline in the ORR activity. However, other types of OH* adsorption on Fe in the form of HO*FeOH and *FeOH intermediates cannot cause the protonation of N or any breaking of Fe–N bonds in the FeN₄ moiety, only inducing the blocking of the Fe site. Meanwhile, based on the competitive relationship between catalyzing the ORR and Fe site oxidation, we propose a trade-off potential (U^RHE_TMOR) to describe the anti-oxidation abilities of the TM site in the TMN_X moiety during the ORR.

We summarize possible catalyst degradation mechanisms during the ORR. Protonation on an N atom of bare FeNC catalysts is difficult, leaching of the Fe site is also likely to happen, due to successive N protonation that destroys the FeN₄ moiety releasing Fe(OH)₂ species.     

On a generalized taylor theorem: A rational proof of the validity of the homotopy analysis method

IntroductionIn 1 7thcenturyIsaacNewton[1]gavesuchabinomialexpressionforfractionalandnegativeexponents(1 +t) α,i.e.,(1 +t) α =1 + +∞k=1α(α-1 ) (α-2 )… (α -k+ 1 )k !tk　　 (α≠ 0 ,1 ,2 ,… ) ,(1 )whoseconvergenceradiusisone.Furthermore ,theclassicalTaylorseries (seeRef.[2 ] )limm→+∞ mk=0f(k) (z0 )k !(z-z0 ) k (2 )ofacomplexfunctionf(z)atz=z0 isvalidmostlyinarestrictedconvergenceregion｜z-z0 ｜相似文献   

亚半正定阵左右逆特征值问题的进一步研究

１　引　言文［１］研究了亚半正定阵的左右逆特征值问题,它的更一般提法是问题Ｉ给定Ｘ、Ｚ使得其中Ｒｎ×ｍ表示全体ｎ×ｍ实阵的集合;即表示全体亚半正定阵集合［２］．文［１］得到了问题１有解的充要条件及解的通式,但从文［１］中主要定理给出的通式来看,子矩阵Ａ１３、Ａ１４及Ａ４３的表达式还没有得到,因此有必要对问题Ⅰ的通解作进一步的研究．本文将通过建立一个亚半正定阵的判定准则,圆满地解决以上问题． 为方便起见,本文用 及Ⅰ分别表示Ｒｎ×ｍ中秩为ｒ的矩阵集合、ｎ×正交矩阵集合及单位矩阵;而用　分别表示ｎ ×…