A SN2 reaction that avoids its deep potential energy minimum

Chemical dynamics trajectory simulations were used to study the atomic-level mechanisms of the OH- + CH3F --> CH3OH + F- SN2 nucleophilic substitution reaction. The reaction dynamics, from the [OH...CH3...F]- central barrier to the reaction products, are simulated by ab initio direct dynamics. The reaction's potential energy surface has a deep minimum in the product exit channel arising from the CH3OH...F- hydrogen-bonded complex. Statistical theories of unimolecular reaction rates assume that the reactive system becomes trapped in this minimum and forms an intermediate, with random redistribution of its vibrational energy, but the majority of the trajectories (90%) avoided this potential energy minimum and instead dissociated directly to products. This finding is discussed in terms of intramolecular vibrational energy redistribution (IVR) and the relation between IVR and molecular structure. The finding of this study may be applicable to other reactive systems where there is a hierarchy of time scales for intramolecular motions and thus inefficient IVR.     

Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex

Cleavage of the relatively inert dinitrogen (N(2)) molecule, with its extremely strong N identical withN triple bond, has represented a major challenge to the development of N(2) chemistry. This report describes the reductive cleavage of N(2) to two nitrido (N(3-)) ligands in its reaction with Mo(NRAr)(3), where R is C(CD(3))(2)CH(3) and Ar is 3,5-C(6)H(3)(CH(3))(2'), a synthetic three-coordinate molybdenum(III) complex of known structure. The formation of an intermediate complex was observed spectroscopically, and its conversion (with N identical withN bond cleavage) to the nitrido molybdenum(VI) product N identical withMo(NRAr)(3) followed first-order kinetics at 30 degrees C. It is proposed that the cleavage reaction proceeds by way of an intermediate complex in which N(2) bridges two molybdenum centers.     

Atom collision-induced resistivity of carbon nanotubes

We report the observation of unusually strong and systematic changes in the electron transport in metallic single-walled carbon nanotubes that are undergoing collisions with inert gas atoms or small molecules. At fixed gas temperature and pressure, changes in the resistance and thermopower of thin films are observed that scale as roughly M(1/3), where M is the mass of the colliding gas species (He, Ar, Ne, Kr, Xe, CH4, and N2). Results of molecular dynamics simulations are also presented that show that the maximum deformation of the tube wall upon collision and the total energy transfer between the colliding atom and the nanotube also exhibit a roughly M(1/3) dependence. It appears that the transient deformation (or dent) in the tube wall may provide a previously unknown scattering mechanism needed to explain the atom collision-induced changes in the electrical transport.     

Direct kinetic measurements of Criegee intermediate (CH₂OO) formed by reaction of CH₂I with O₂

Ozonolysis is a major tropospheric removal mechanism for unsaturated hydrocarbons and proceeds via "Criegee intermediates"--carbonyl oxides--that play a key role in tropospheric oxidation models. However, until recently no gas-phase Criegee intermediate had been observed, and indirect determinations of their reaction kinetics gave derived rate coefficients spanning orders of magnitude. Here, we report direct photoionization mass spectrometric detection of formaldehyde oxide (CH(2)OO) as a product of the reaction of CH(2)I with O(2). This reaction enabled direct laboratory determinations of CH(2)OO kinetics. Upper limits were extracted for reaction rate coefficients with NO and H(2)O. The CH(2)OO reactions with SO(2) and NO(2) proved unexpectedly rapid and imply a substantially greater role of carbonyl oxides in models of tropospheric sulfate and nitrate chemistry than previously assumed.     

Watching vibrational energy transfer in liquids with atomic spatial resolution

Ultrafast spectroscopy was used to study vibrational energy transfer between vibrational reporter groups on different parts of a molecule in a liquid. When OH stretching vibrations of different alcohols were excited by mid-infrared laser pulses, vibrational energy was observed to move through intervening CH2 or CH groups, taking steps up and down in energy, ending up at terminal CH3 groups. For each additional CH2 group in the path between OH and CH3, the time for vibrational energy transfer increased by about 0.4 picosecond.     

中国稻田CH_4和N_2O排放及减排整合分析

【目的】对中国有关稻田CH4和N2O排放试验结果进行整合分析,估算不同管理措施的减排潜力,为稻田CH4和N2O减排提供参考依据。【方法】通过建立中国稻田CH4和N2O排放的数据库,研究稻田CH4和N2O的排放特征,分析作用显著的影响因素,比较不同措施的减排效果。【结果】中国稻田CH4排放存在明显的地域性分布规律,主要表现为西南地区稻田CH4排放远高于其它地区。水稻生长季节水分管理方式、非水稻生长季水分状态、化肥氮投入量和有机物料对稻田CH4排放具有重要影响(P0.05)。与淹水灌溉(CF)相比,前期淹水-中期晒田-淹水(F-D-F)、前期淹水-中期晒田-淹水-湿润灌溉(F-D-F-M)和间歇灌溉或完全湿润(M)降低稻田CH4排放的幅度分别为45%、59%和83%。与休闲期淹水(F)相比,采取冬闲期排干(SD)、稻旱轮作(LD)或旱-旱-稻轮作模式(TD),能降低稻田CH4排放42%—56%。不同有机添加物产生CH4的能力的顺序为:作物秸秆+厩肥(S+FM)绿肥(GM)厩肥(FM)作物秸秆(S)堆肥或沼渣(CM)。化学氮肥的种类对CH4排放有一定的影响,但特征不明显,而随着氮肥用量(N)的增加,CH4排放逐渐降低。当0N≤150kgN·hm-2,150N250kgN·hm-2和≥250kgN·hm-2时,CH4排放较不施任何肥料降低12%、29%和65%。中国稻田N2O排放的地域性分布特征不明显。水稻生长季节水分管理方式、非水稻生长季水分状态和总氮投入量是影响N2O排放的最重要的因素(P0.05)。与CF相比,F-D-F、F-D-F-M和M能够提高稻田N2O排放12%、140%和478%,而且在F-D-F、F-D-F-M模式下的氮肥N2O排放因子分别为0.43%和0.68%。不同非水稻生长季水分状态模式下N2O排放平均值表明,SD、LD和TD比F增加40%—110%的排放。【结论】稻田CH4和N2O排放的消长关系表现在水分管理、非水稻生长季节的水分状态和氮素的投入量等方面。合理的减排措施应基于二者的综合考虑。通过优化稻田水肥管理措施可降低稻田CH4和N2O排放的温室效应。     

小偃麦衍生品系CH7086对白粉病抗性的遗传分析

CH7086是衍生于十倍体长穗偃麦草与普通小麦的八倍体"小偃7430"的小麦新品系,对小麦白粉病和条锈病均为免疫。为明确其白粉病抗性的遗传规律,用高感品种(系)绵阳11,晋太170,CH5241与CH7086杂交,将其F1,F2及其亲本分别在太原温室(用白粉病15号小种的E09菌系接种)进行了抗性基因的遗传分析。结果表明:F1对白粉病的感染为0级。F2群体中,白粉病抗感分离符合3R:1S,说明小偃麦衍生品系CH7086对白粉病的抗性受1对显性基因控制。     

有机肥对日光温室生菜地土壤温室气体排放的影响

采用静态箱-气相色谱法研究日光温室生菜地不施肥(CK)、施用腐熟鸡粪(H)、羊粪(S)、鸡粪+秸秆(HSt)、羊粪+秸秆(SSt)、羊粪+鸡粪+秸秆(SHSt)等6种处理的温室气体排放通量及增温潜势(GWP)。结果表明:(1)H、S、HSt处理的N_2O排放通量在施肥前、中、后期呈近"V"型变化,CK、SSt、SHSt呈倒"V"型变化;S、SSt、SHSt处理的CH_4排放通量呈倒"V"型变化;CO_2排放通量均呈近"V"型变化(SSt除外);(2)施肥前期,HSt、S、H、SHSt、SSt处理的N_2O排放通量分别较CK显著增加2.89、2.32、1.48、1.17、0.95倍;S、H的CH_4排放通量显著高于CK处理1.91、1.11倍;H的CO_2排放通量显著低于CK处理3.88倍。施肥中期,HSt的N_2O排放通量显著低于CK处理1.93倍;SHSt的CH_4排放通量显著高于CK处理1.34倍;各施肥处理的CO_2排放通量与CK差异不显著。施肥后期,H的N_2O排放通量显著高于CK处理1.10倍;SHSt、SSt、S的CH_4排放通量显著低于CK处理3.76、5.25、5.58倍;HSt的CO_2排放通量显著高于CK处理8.61倍;(3)全球增温潜势(GWP)按照SSHStHStSStCKH依次减小,建议施用腐熟鸡粪、鸡粪加秸秆及羊粪加秸秆。     

The process of tholin formation in Titan's upper atmosphere

Titan's lower atmosphere has long been known to harbor organic aerosols (tholins) presumed to have been formed from simple molecules, such as methane and nitrogen (CH4 and N2). Up to now, it has been assumed that tholins were formed at altitudes of several hundred kilometers by processes as yet unobserved. Using measurements from a combination of mass/charge and energy/charge spectrometers on the Cassini spacecraft, we have obtained evidence for tholin formation at high altitudes (approximately 1000 kilometers) in Titan's atmosphere. The observed chemical mix strongly implies a series of chemical reactions and physical processes that lead from simple molecules (CH4 and N2) to larger, more complex molecules (80 to 350 daltons) to negatively charged massive molecules (approximately 8000 daltons), which we identify as tholins. That the process involves massive negatively charged molecules and aerosols is completely unexpected.     

Prebiotic synthesis of methionine

Methionine has been shown to be a product of the action of a spark discharge on a simulated primitive earth atmosphere containing CH(4), N(2), NH(3), H(2)O, and H(2)S or CH(3)SH. Acrolein has also been shown to be a product of the discharge and is proposed as an intermediate in the prebiotic synthesis of methionine and of glutamic acid, homocysteine, homoserine, and alpha,gamma-diaminobutyric acid.     

Synthesis and structure of a terminal uranium nitride complex

The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex [UN(Tren(TIPS))][Na(12-crown-4)(2)] {in which Tren(TIPS) = [N(CH(2)CH(2)NSiPr(i)(3))(3)](3-) and Pr(i) = CH(CH(3))(2)} by reaction of the uranium(III) complex [U(Tren(TIPS))] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of (15)N-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water.     

A mercury-catalyzed, high-yield system for the oxidation of methane to methanol

A homogeneous system for the selective, catalytic oxidation of methane to methanol via methyl bisulfate is reported. The net reaction catalyzed by mercuric ions, Hg(II), is the oxidation of methane by concentrated sulfuric acid to produce methyl bisulfate, water, and sulfur dioxide. The reaction is efficient. At a methane conversion of 50 percent, 85 percent selectivity to methyl bisulfate ( approximately 43 percent yield; the major side product is carbon dioxide) was achieved at a molar productivity of 10(-7) mole per cubic centimeter per second and Hg(II) turnover frequency of 10(-3) per second. Separate hydrolysis of methyl bisulfate and reoxidation of the sulfur dioxide with air provides a potentially practical scheme for the oxidation of methane to methanol with molecular oxygen. The primary steps of the Hg(II)-catalyzed reaction were individually examined and the essential elements of the mechanism were identified. The Hg(II) ion reacts with methane by an electrophilic displacement mechanism to produce an observable species, CH(3)HgOSO(3)H, 1. Under the reaction conditions, 1 readily decomposes to CH(3)OSO(3)H and the reduced mercurous species, Hg(2)(2+) The catalytic cycle is completed by the reoxidation of Hg(2)(2+) with H(2)SO(4) to regenerate Hg(II) and byproducts SO(2) and H(2)O. Thallium(III), palladium(II), and the cations of platinum and gold also oxidize methane to methyl bisulfate in sulfuric acid.     

Coupling of nitrous oxide and methane by global atmospheric chemistry

Nitrous oxide (N(2)O) and methane (CH(4)) are chemically reactive greenhouse gases with well-documented atmospheric concentration increases that are attributable to anthropogenic activities. We quantified the link between N(2)O and CH(4) emissions through the coupled chemistries of the stratosphere and troposphere. Specifically, we simulated the coupled perturbations of increased N(2)O abundance, leading to stratospheric ozone (O(3)) depletion, altered solar ultraviolet radiation, altered stratosphere-to-troposphere O(3) flux, increased tropospheric hydroxyl radical concentration, and finally lower concentrations of CH(4). The ratio of CH(4) per N(2)O change, -36% by mole fraction, offsets a fraction of the greenhouse effect attributable to N(2)O emissions. These CH(4) decreases are tied to the 108-year chemical mode of N(2)O, which is nine times longer than the residence time of direct CH(4) emissions.     

Observation of transition-state vibrational thresholds in the rate of dissociation of ketene

Rate constants for the dissociation of highly vibrationally excited ketene (CH(2)CO) have been measured at the threshold for the production of CH(2)((3)B(1)) and CO((1)Sigma(+)). The rate constant increases in a stepwise manner with increasing energy, consistent with the long-standing premise that the rate of a unimolecular reaction is controlled by flux through quantized transition-state thresholds. The data give the energies of the torsional and C-C-O bending vibrations of the transition state.     

Quantification of primary versus secondary C-h bond cleavage in alkane activation: propane on pt

The trapping-mediated dissociative chemisorption of three isotopes of propane (C(3)H(8), CH(3),CD(2)CH(3), and C(3)D(8)) has been investigated on the Pt(110)-(1 x 2) surface, and both the apparent activation energies and the preexponential factors of the surface reaction rate coefficients have been measured. In addition, the probabilities of primary and secondary C-H bond cleavage for alkane activation on a surface were evaluated. The activation energy for primary C-H bond cleavage was 425 calories per mole greater than that of secondary C-H bond cleavage, and the two true activation energies that embody the single measured activation energy were determined for each of the three isotopes. Secondary C-H bond cleavage is also preferred on entropic grounds, and the magnitude of the effect was quantified.     

Silver-catalyzed C-C bond formation between methane and ethyl diazoacetate in supercritical CO₂

Even in the context of hydrocarbons' general resistance to selective functionalization, methane's volatility and strong bonds pose a particular challenge. We report here that silver complexes bearing perfluorinated indazolylborate ligands catalyze the reaction of methane (CH(4)) with ethyl diazoacetate (N(2)CHCO(2)Et) to yield ethyl propionate (CH(3)CH(2)CO(2)Et). The use of supercritical carbon dioxide (scCO(2)) as the solvent is key to the reaction's success. Although the catalyst is only sparingly soluble in CH(4)/CO(2) mixtures, optimized conditions presently result in a 19% yield of ethyl propionate (based on starting quantity of the diazoester) at 40°C over 14 hours.     

水稻品种对三江平原稻田温室气体排放的影响

利用静态箱一气相色谱法研究了三江平原3个主栽水稻品种(空育131、龙粳18、垦鉴稻6)对生长季节稻田CO2、CH4和N2O排放规律、源/汇及其与环境因子关系的影响.结果表明:3个水稻品种的CO2、CH4和N2O平均通量范围分别为405.5 ～ 647.2、9.6 ～20.5 mg·m-2·h-1、4.1 ～6.3 μg...     

东北季节性冻融农田土壤CO2、CH4、N2O通量特征研究

为了评估季节性冻融交替对土壤温室气体排放的影响,采用静态暗箱-气相色谱法,监测了东北松嫩平原两种典型农田生态系统(稻田和玉米田)非生长季土壤CO_2、CH_4和N_2O通量变化。研究表明:三种温室气体排放在土壤冻结期、覆雪期、融雪期和解冻期具有明显的季节动态特征。冻结期和融雪期对温室气体排放贡献最大,这两个时期内稻田和玉米田CO_2排放量分别占非生长季总累积排放量的74.9%和68.6%,稻田CH_4排放占非生长季总排放的95.7%,尽管玉米田土壤CH_4以吸收为主,但在融雪过程中存在明显释放峰,短暂的融雪期内N_2O呈集中爆发性释放,稻田和玉米田N_2O通量峰值分别是冻结前的40倍和99倍,排放量占到总累积排放量的73.9%和80.7%,覆雪期土壤CH_4和N_2O存在弱的吸收。另外,土壤温室气体排放存在土地利用方式间的差异,表现在稻田土壤比玉米田(非生长季)具有更高的温室气体排放潜力。稻田土壤CO_2、CH_4和N_2O累积排放量均高于玉米田,表现为净排放(源),而玉米田土壤CH_4通量表现为净吸收(汇);稻田土壤CO_2和CH_4平均排放速率显著高于玉米田;除覆雪期外,其他时期内三种温室气体平均通量在两类农田之间也存在显著差异。总之,在评价季节性冻土区温室气体排放时需要重视土壤冻结和融化过程,同时需要考虑不同土地利用方式间的差异。     

Reactions of oriented molecules

Beams of oriented molecules have been used to directly study geometrical requirements in chemical reactions. These studies have shown that reactivity is much greater in some orientations than others and demonstrated the existence of steric effects. For some reactions portions of the orientation results are in good accord with traditional views of steric hindrance, but for others it is clear that our chemical intuition needs recalibrating. Indeed, the information gained from simultaneously orienting the reactants and observing the scattering angle of the products may lead to new insights about the detailed mechanism of certain reactions. Further work must be done to extend the scope and detail of the studies described here. More detailed information is needed on the CH(3)I reaction and the CF(3)I reaction. The effects of alkyl groups of various sizes and alkali metals of various sizes are of interest. In addition, reactions where a long-lived complex is formed should be studied to see if orientation is important. Finally, it would be of interest to apply the technique to the sort of reactions that led to our interest in the first place: the S(N)2 displacements in alkyl halides where the fascinating Walden inversion occurs.