Pd2X2（dpm）2（X=NCO^—,CH3CO2^—,SCN^—,NO^—3;dpm=Ph2PCH2PPh2）配合…

采用ＮＭＲ方法考察了室温和低温（－７８～－６０℃）下Ｐｄ２Ｘ２（ｄｐｍ）２（Ｘ＝ＮＣＯ＾－，ＣＨ３ＣＯ＾－２，ＳＣＮ＾－和ＮＯ＾－３，ｄｐｍ＝Ｐｈ２ＰＣＨ２ＰＰｈ２）与Ｈ２Ｓ在ＣＤ２Ｃｌ２或ＣＤＣｌ３中的反应。结果表明，在Ｘ＝ＮＣＯ＾－和ＣＨ３ＣＯ＾－２的情况下，Ｈ２Ｓ优先与这些Ｐｄ配合物的阴离子作用生成相应的共轭酸ＨＸ和Ｐｄ２（ＳＨ）２（ｄｐｍ）２，后者在Ｈ２Ｓ存在下又进一步转化为Ｐｄ２（ＳＨ）     

CIONO2与O(3P)的反应机理

采用密度泛函方法Ｂ３ＬＹＰ／６－３１Ｇ＾＊研究了反应Ｏ（＾３Ｐ）＋ＣｌＯＮＯ２→ＣｌＯ＋ＮＯ３反应Ｏ（＾３Ｐ）＋ＣｌＯＮＯ２→Ｏ２＋ＣｌＯＮＯ的反应机。该结果与大部分实验者的推论是一致的,对于后一反应,其两种反应途径的活化势垒较为相近,表明两种反应途径均是可能的。     

等瓣置换反应的研究——手性簇合物[η^—MeO2CC5H4）（CO）2Mo…

用Ｘ射线衍微法测定了由η＾５－ＭｅＯ２ＣＣ５Ｈ４（ＣＯ）３ＭｏＮａ和〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ－（ＣＯ）３Ｃｏ（ＣＯ）３（μ３－Ｓ）的等瓣置换反应所生成的手性簇合物－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｍｏ〕－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ（ＣＯ）３（μ３－Ｓ）的分子结构及晶体结构。晶体属Ｐ１空间群，晶胞参数ａ＝０．８７１６２（５）ｎｍ，ｂ＝０．８     

LaX3-C18H16N3O2Cl-H2O三元体系的相平衡

测定了ＬａＸ３－Ｃ１８Ｈ１６Ｎ３Ｏ２Ｃｌ－Ｈ２Ｏ（Ｘ＝ＮＯ＾３,Ｃｌ＾－）三元体系在３０℃时的溶度和饱和溶液的折光率。发现Ｌａ（ＮＯ３）３＝Ｃ１８Ｈ１６Ｎ３Ｏ２Ｃｌ－Ｈ２Ｏ体系有不一致溶化合物Ｌａ（Ｃ１８Ｈ１６Ｎ３Ｏ２Ｃｌ）３（ＮＯ３）３生成,而ＬａＣｌ３－Ｃ１８Ｈ１６Ｎ３Ｏ２Ｃｌ－Ｈ２Ｏ体系为简单共饱体系。     

稀土铕与2—[（取代苯胺基）羰基]苯甲酸配合物的研究

报道了配合物Ｅｕ（ＸｎＰ）３．３Ｈ２Ｏ「其中Ｘ＝Ｈ，２－Ｃｌ，３－ＯＨ，４－Ｂｒ，３－ＮＯ２，２－ＯＣＨ３，２－ＣＨ３，２，４－二氯；Ｐ＝２－（ＣＯＯ）Ｃ６Ｈ４ＣＯＮＨＣ６Ｈ５－＾－，ｎ＝１，２」的制备，并用元素分析，红外光谱，电子反射光谱，热重分析进行了表征。     

电子激发态CH（C^2Σ^＋）自由基的猝灭速率常数的测定

用２６６ｎｍ激光光解ＣＨＢｒ３分子产生ＣＨ（Ｃ）态自由基，通过测量ＣＨ（Ｃ＾２Σ＾＋→Ｘ＾２Ⅱ）的总荧光信号强度来测定室温下Ｏ２、Ｎ２、ｎ－Ｃ５Ｈ１２、ｎ－Ｃ６Ｈ１４和ｎ－Ｃ７Ｈ１６对ＣＨ（Ｃ２Σ＾＋，ｖ′＝０）的猝灭常数。结果表明，这些碰撞伴侣（Ｏ２和Ｎ２例外）对ＣＨ（Ｘ、Ａ、Ｂ和Ｃ）的反应或猝灭速率常数ｋ存在下列关系：ｋ（Ｘ）〉ｋ（Ｂ）〉ｋ（Ａ）≈ｋ（Ｃ），且烷烃分子对ＣＨ（Ｃ）态的猝灭速率常     

CH3与NO在单、三态势能面上的反应机理

用从头算分了轨道法，在ＵＨＦ／６－３１Ｇ，水平上研究了ＣＨ３Ｏ与ＮＯ在单、三态势能面上的反应机理，发现该反应在两个势能面上均在两个彼此平行的反应途径，分别生产成产物ＣＨ３ＯＮ（ａ）和ＨＣＨＯ＋ＨＮＯ（ｂ），优化了四个途径的所有驻点的几何构型，用Ｍｏｒｏｋｕｍａ的数值分析方法计算了它们的内禀反应坐标（ＩＲＣ），各途径经零点能（ＺＰＥ）校正的活化位垒，单重态途径（ａ）为８６．８６ｋＪ．ｍｏｌ＾－１途径     

N—甲基吡咯烷酮与HnXW12O40.mH2O（X=P,Si,Ge）电荷转移盐的合成 …

由Ｎ－甲基吡咯烷酮和ＨｎＸＷ１２Ｏ４０．ｍＨ２Ｏ（Ｘ＝Ｐ,Ｓｉ,Ｇｅ）合成了具有非线性光学性能的电荷转移盐,（ＮＭＰＨ）３ＰＷ１２Ｏ４０．ＣＨ３ＣＮ（Ⅰ）（ＮＭＰＨ）ＳｉＷ１２Ｏ４０．ＣＨ３ＣＮ（Ⅱ）和（ＮＭＰＨ）４ｅＷ１２Ｏ４０．ＣＨ３ＣＮ（Ⅲ）。并由元素分析,红外光谱,漫反射电子光谱进行了表征。结果表明杂多酸形成电荷转移盐后其阴离子结构未变;Ｎ－甲基吡咯烷酮通过Ｎ原子与酸中的质子Ｈ＾＋ＸＦＳＱ     

[Mx(FeCO2)yLz]型配合物的合成、表征及CV性质研究(M＝Cu(II), Co(II), Cd(II), Pb(II);L=THF, Cl-)

［Ｍｘ（ＦｃＣＯ２）ｙＬｘ］型配合物可在ＴＨＦ中通Ｎ２条件下由ＦｃＣＯ２Ｈ和ＭＸ．ｎＨ２Ｏ（Ｘ＝Ｃｌ＾－和Ａｃ＾－）经长时间反应制得。ＩＲ和＾１ＨＮＭＲ谱表明Ｃｕ（Ⅱ）、Ｃｏ（Ⅱ）属螯环配合物，Ｃｄ（Ⅱ）属四面体型配合物，Ｐｂ（Ⅱ）属线型化合物。     

CH2(X 3B1)自由基与O2的反应

用时间分辨富里叶红外发射谱仪（ＴＲ－ＦＴＩＲＳ）研究了ＣＨ２（Ｘ＾３Ｂ１）自由基与Ｏ２反应的通道及产物的振动动态布居，基电子态自由基ＣＨ２（Ｘ＾３Ｂ１）由３５１ｎｍ紫外激光光解ＣＨ２ＣＯ生成，观测到振动发态反应产物ＣＯ（ｖ≤１０），ＣＯ２（ｖ３≤７）ＯＨ（Ｈ２Ｏ）和Ｈ２ＣＯ的红外发射，证实存在生成Ｈ２ＣＯ的通道，由光谱拟合得到不同时刻ＣＯ（ｖ）和ＣＯ２（ｖ３）的相对振动布居，发现ｖ＝４能级的布居数     

A theoretical study of the mechanism and kinetics of F+N3 reactions.

Both the singlet(1A') and triplet(3A') potential energy surfaces (PESs) of F+N(3) reactions are investigated using the complete-active-space self-consistent field (CASSCF) and the multireference configuration interaction (MRCI) methods with a proper active space. The minimum energy crossing point (MECP) at the intersection seam between the 1A' and 3A' PESs is located and used to clarify the reaction mechanisms. Two triplet transition states are found, with one in the cis form and the other one in the trans form. Further kinetic calculations are performed with the canonical unified statistical (CUS) theory on the singlet PES and the improved canonical variational transition-state (ICVT) method on the triplet PES. The rate constants are also reported. At 298 K, the calculated rate constant is in reasonably good agreement with experimental values, and spin-orbit coupling effects lower it by 28 %. The spectroscopic constants derived from the fitted potential-energy curves for the singlet and triplet states of NF are in very good agreement with experimental values. Our calculations indicate that the adiabatic reaction on the singlet PES leading to NF(a(1)Delta)+N(2) is the major channel, whereas the nonadiabatic reaction through the MECP, which leads to NF(X(3)Sigma(-))+N(2), is a minor channel.     

HNCS与CH2(X2Π)反应微观动力学的理论研究

用量子化学密度泛函理论的UB3LYP/6-311+G**方法和高级电子相关的UQCISD(T)/6-311+G**方法研究了异硫氰酸(HNCS)与乙炔基自由基(C2H(X2Π))反应的微观机理. 采用双水平直接动力学方法IVTST-M, 获取反应的势能面信息, 应用正则变分过渡态理论并考虑小曲率隧道效应, 计算了在250～2500 K温度范围内反应的速率常数. 研究结果表明, HNCS与C2H(X2Π)反应为多通道、多步骤的复杂反应, 共存在三个可能的反应通道, 主反应通道为通过分子间H原子迁移, 生成主要产物NCS+C2H2. 反应速率常数随温度升高而增大, 表现为正温度效应. 速率常数计算中变分效果很小. 在低温区隧道效应对反应速率的贡献较大, 反应为放热反应.     

活性氮与SO2和SOCl2的传能反应

在流动余辉装置上, 研究了活性氮与SO2和SOCl2之间的反应过程. 在280～500 nm, 观察到了SO2( A1A2,B1B1→X1A1 )和SO2(a3B1→X1A1)的发射光谱. 对比由Ar(3P0,2)与N2碰撞反应产生的纯N2(A3Σu+)与SO2、SOCl2之间反应的实验结果, 可以说明, N2(A3Σu+)在活性氮与SO2的反应中是主要的能量载体, 它与SO2的直接能量转移反应形成了激发态的SO2(A1A2, B1B1); 在活性氮与SOCl2的反应中观测到的激发态SO2(a3B1), 则可能主要是通过N(4S)与SOCl2反应生成的N2O(X1Σ+)和N2(A3Σu+)与SOCl2反应生成的SO(X3Σ－)之间的化学反应过程产生.     

A crossed beams study of the reaction of carbon atoms, C(3Pj), with vinyl cyanide, C2H3CN(X 1A')--investigating the formation of cyano propargyl radicals

The chemical dynamics of the reaction of ground state carbon atoms, C(3Pj), with vinyl cyanide, C2H3CN(X 1A'), were examined under single collision conditions at collision energies of 29.9 and 43.9 kJ mol(-1) using the crossed molecular beams approach. The experimental studies were combined with electronic structure calculations on the triplet C4H3N potential energy surface (H. F. Su, R. I. Kaiser, A. H. H. Chang, J. Chem. Phys., 2005, 122, 074320). Our investigations suggest that the reaction follows indirect scattering dynamics via addition of the carbon atom to the carbon-carbon double bond of the vinyl cyanide molecule yielding a cyano cyclopropylidene collision complex. The latter undergoes ring opening to form cis/trans triplet cyano allene which fragments predominantly to the 1-cyano propargyl radical via tight exit transition states; the 3-cyano propargyl isomer was inferred to be formed at least a factor of two less; also, no molecular hydrogen elimination channel was observed experimentally. These results are in agreement with the computational studies predicting solely the existence of a carbon versus hydrogen atom exchange pathway and the dominance of the 1-cyano propargyl radical product. The discovery of the cyano propargyl radical in the reaction of atomic carbon with vinyl cyanide under single collision conditions implies that this molecule can be an important reaction intermediate in combustion flames and also in extraterrestrial environments (cold molecular clouds, circumstellar envelopes of carbon stars) which could lead to the formation of cyano benzene (C6H5CN) upon reaction with a propargyl radical.     

二氧化钚分子的多体展式势能函数

从导出基态PuO2分子的电子状态X5Σ g正确地判断其离解极限出发,采用MP2方法,应用相对论有效原子实模型(RECP)优化出PuO2(X5Σ g)分子稳定构型为线性OPuO(D∞h),其平衡核间距Re=0.18004nm.同时也计算出振动频率,并优化出存在亚稳态的Pu-O-O(C∞v)构型.使用多体项展式理论方法,导出了基态PuO2分子的分析势能函数.该势能表面准确地再现了O-Pu-O(D∞h)平衡结构和亚稳态的Pu-O-O(C∞v)构型.然后根据势能函数等值图讨论了O(3Pg) PuO反应的势能面静态特征.     

活性氮反应产生激发态卤化氮实验研究

A new method for producing electronically excited nitrogen monohalides NX(b) (X=F,Cl,Br) is reported. The strong emission spectra of NBr(b1Σ+→X3Σ–) are observed when alkyl bromides (CHBr3, CH2Br2, C2H5Br, and C4H9Br) are added to a stream of active nitrogen, generated by a hollow-cathode discharge of N2, in a flowing afterglow system. Some tentative experiments show that the electronically excited NBr(b) is formed by means of metastable N2(A3Σu+) Electronic-to-Electronic energy transfer to NBr(X), which is from the reaction of N(4S) with alkyl bromides. The emission spectra of NCl(b1Σ+→X3Σ–) are obtained when CCl4 or SOCl2 is admitted into a flow of active nitrogen, but neither CHCl3 nor CH2Cl2 addition results in such an emission. It has been proposed that the origin of the excited NCl(b) is an energy transfer from N2 (A) to NCl(X), generated by the reaction of N(4S) with CCl3 (or SOCl2). Similar experiments are also carried out with SF6 as reagent of active nitrogen, or as mixture with N2 in the discharge. By recording fluorescence it was found that excited NF(b) is produced only under discharge through N2/SF6 mixture. The NF(b) state presumably arises from the energy transfer from N2(A) to NF(X), and the latter is generated from the abstraction of fluorine by N(4S) from SF5.     

New ab initio potential energy surface and quantum dynamics of the reaction H(2S) + NH(X3Σ-) → N(4S) + H2

A new global potential energy surface is reported for the ground state ((4)A(")) of the reaction H((2)S) + NH(X(3)Σ(-)) → N((4)S) + H(2) from a set of accurate ab initio data, which were computed using the multi-reference configuration interaction with a basis set of aug-cc-pV5Z. The many-body expansion and neural network methods have been used to construct the new potential energy surface. The topographical features of the new global potential energy surface are presented. The predicted barrier height is lower than previous theoretical estimates and the heat of reaction with zero-point energy is closer to experimental results. The quantum reactive scattering dynamics calculation was carried out over a range of collision energies (0-1.0 eV) on the new potential energy surface. The reaction probabilities, integral cross-section, and rate constants for the title reaction were calculated. The calculated rate constants are in excellent agreement with the available experimental results.     

Mechanism and kinetics of the atmospheric degradation of perfluoropolymethylisopropyl ether by OH radical: a theoretical study

In the present work, the mechanism and kinetics of the reaction of perfluoropolymethylisopropyl ether (PFPMIE) with OH radical are studied. The reaction between PFPMIE and OH radical is initiated through breaking of C–C or C–O bond of PFPMIE. These reactions lead to the formation of COF₂ molecules and alkyl radical. The pathways corresponding to the reaction between PFPMIE and OH radical have been modelled using density functional theory methods M06-2X and MPW1K with 6-31G(d,p) basis set. It is found that the C–C bond breaking reaction is most favourable than the C–O bond breaking reaction. The subsequent reactions of the alkyl radicals, formed from the C–C bond breaking reactions, are studied in detail. The rate constant for the initial oxidation reactions is calculated using canonical variational transition state theory with small curvature tunnelling corrections over the temperature range of 278–350 K. From the calculated reaction, potential energy surface and rate constant, the lifetime and global warming potential of PFPMIE are studied.     

Insights into the structure and reactivity of acylperoxo complexes in the Kochi-Jacobsen-Katsuki catalytic system. A density functional study

Structural properties of the acylperoxo complexes [(Salen)Mn(III)RCO(3)] (2) and [(Salen)Mn(IV)RCO(3)] (3), the critical intermediates in the Kochi-Jacobsen-Katsuki reaction utilizing organic peracids or O(2)/aldehydes as oxygen source, have been studied with the density functional theory. Four distinct isomers, cis(O,N), cis(N,O), cis(N,N), and trans, of these complexes have been located. The isomer 2-cis(O,N) in its quintet ground state, and nearly degenerate isomers 3-cis(O,N) and 3-cis(N,O) in their quartet ground states are found to be the lowest in energy among the other isomers. The O-O bond cleavage in the cis(O,N), cis(N,O), and trans isomers of 2 and 3 has been elucidated. In complex 3, the O-O bond is inert. On the contrary, in complex 2, the O-O bond cleaves via two distinct pathways. The first pathway occurs exclusively on the quintet potential energy surface (PES) and corresponds to heterolytic O-O bond scission coupled with insertion of an oxygen atom into an Mn-N(Salen) bond to form 2-N-oxo species; this pathway has the lowest barrier of 14.9 kcal/mol and is 15.6 kcal/mol exothermic. The second pathway is tentatively a spin crossover pathway. In particular, for 2-cis(O,N) and 2-cis(N,O) the second pathway proceeds through a crucial minimum on the seam of crossing (MSX) between the quintet and triplet PESs followed by heterolytic O-O cleavage on the triplet PES, and produces unusual triplet 2-cis(O,N)- and 2-cis(N,O)-oxo ([(Salen)Mn(V)(O)RCO(2)]) species; this pathway requires 12.8 kcal/mol and is 1.4 kcal/mol endothermic. In contrast, for the 2-trans isomer, spin crossing is less crucial and the O-O cleavage proceeds homolytically to generate 2-trans-oxo [(Salen)Mn(IV)(O)] species with RCO(2) radical; this pathway, however, cannot compete with that in 2-cis because it needs 21.9 kcal/mol for activation and is 15.3 kcal/mol endothermic. In summary, the O-O cleavage occurs predominantly in the 2-cis complexes, and may proceed either through pure high spin or spin crossover heterolytic pathway to produce 2-cis-oxo and 2-N-oxo species.     

Theoretical study of the mechanism of NO2 production from NO + ClO

The reaction of NO with ClO has been studied theoretically using density-functional and wave function methods (B3LYP and CCSD(T)). Although a barrier for cis and trans additions could be located at the RCCSD(T) and UCCSD(T) levels, no barrier exists at the B3LYP/6-311+G(d) level. Variational transition state theory on a CASPT2(12,12)/ANO-L//B3LYP/6-311+G(d) surface was used to calculate the rate constants for addition. The rate constant for cis addition was faster than that for trans addition (cis:trans 1:0.76 at 298 K). The rate constant data summed for cis and trans addition in the range 200-1000 K were fit to a temperature-dependent rate in the form kdi) = 3.30 x 10(-13)T(0.558) exp(305/T) cm3.molecule(-1).s(-1), which is in good agreement with experiment. When the data are fit to an Arrhenius plot in the range 200-400 K, an activation barrier of -0.35 kcal/mol is obtained. The formation of ClNO2 from ONOCl has a much higher activation enthalpy from the trans isomer compared to the cis isomer. In fact, the preferred decomposition pathway from trans-ONOCl to NO2 + Cl is predicted to go through the cis-ONOCl intermediate. The trans --> cis isomerization rate constant is kiso = 1.92 x 10(13) exp(-4730/T) s(-1) using transition state theory.