Carbon tunneling from a single quantum state

We observed ring expansion of 1-methylcyclobutylfluorocarbene at 8 kelvin, a reaction that involves carbon tunneling. The measured rate constants were 4.0 x 10(-6) per second in nitrogen and 4 x 10(-5) per second in argon. Calculations indicated that at this temperature the reaction proceeds from a single quantum state of the reactant so that the computed rate constant has achieved a temperature-independent limit. According to calculations, the tunneling contribution to the rate is 152 orders of magnitude greater than the contribution from passage over the barrier. We discuss environmental effects of the solid-state inert-gas matrix on the reaction rate.     

Controlled Deposition of Size-Selected Silver Nanoclusters

Variable-temperature scanning tunneling microscopy was used to study the effect of kinetic cluster energy and rare-gas buffer layers on the deposition process of size-selected silver nanoclusters on a platinum(111) surface. Clusters with impact energies of 相似文献   

Kinetic isotope effects for the reactions of muonic helium and muonium with H2

The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ~4.1 atomic mass units ((4.1)H), because the negative muon almost perfectly screens one proton charge. We report the reaction rate of (4.1)H with (1)H(2) to produce (4.1)H(1)H + (1)H at 295 to 500 kelvin. The experimental rate constants are compared with the predictions of accurate quantum-mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of (0.11)H (where (0.11)H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 kelvin, and variational transition-state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10(-4) to 10(-2) range.     

Quantum low-temperature limit of a chemical reaction rate

The radiation-induced polymerization of formaldehyde has been studied in the solid state. The time of addition of one new link to a polymer chain increases exponentially in accordance with the Arrhenius law at 140 to 80 K, but approaches a constant value (approximately 10(-2) second) at temperatures below 10 K. Thus, a low-temperature limit to a chemical reaction rate has been observed. It is interpreted as a quantum effect caused by tunneling from the zero vibration level of the initial state, and a semiquantitative theory is given. The phenomenon should be taken into account for understanding tunneling of electrons in biological systems when such tunneling is accompanied by conformational changes. It could also be significant in slow, exothermic chemical reactions at low and ultralow temperatures, which may have had a role in chemical and biological evolution (cold prehistory of life?).     

AlH2P3O10·2H2 O（Ⅰ）对水中Ni^2＋的吸附动力学和热力学研究

采用静态吸附法研究Al2O3-P2O5-H2O反应体系产物三聚磷酸二氢铝Ⅰ型二水物[AlH2P3O10.2H2O（Ⅰ）]吸附水中Ni2＋的动力学和热力学。考察了温度、浓度、粒径、pH和搅拌速度对吸附过程的影响,通过不同温度下的吸附等温热力学性能的变化,计算了吸附焓、吸附熵和自由能。结果表明,在试验范围内,AlH2P3O10.2H2O（Ⅰ）对Ni2＋的吸附符合Langmuir吸附等温方程式,过程受颗粒扩散控制,反应级数为1.88,298.15 K时的热力学数据为：Ea=11.561 kJ/mol,ΔH=35.75 kJ/mol,ΔS=190.58 J/（mol.K）,ΔG=-21.07 kJ/mol,吸附为自发的吸热过程,其吸附动力学总方程为：1-2/3x-（1-x）2/3=0.36r02C01.88exp（-11 561/RT）。     

不同介质中石油污染物吸附过程的动力学及热力学研究

以3个不同地域的土壤为研究对象,采用平衡振荡法,研究了石油污染物在不同土壤中的吸附动力学和热力学特征。试验数据分别采用4种动力学模型进行拟合。结果表明,不同土壤对石油污染物的吸附均表现为快反应和慢反应2个阶段,0～15 min为快反应阶段,吸附量达到饱和吸附量的85%。3种土壤对石油污染物的吸附动力学符合拉格朗日假二级动力学方程。不同温度下3种供试土的吉布斯自由能变均为负值,3种土壤对石油污染物吸附过程的焓变、熵变依次为:ΔH029.11、29.12、52.70 kJ/mol;ΔS0-100.85、-103.09、-182.66 J/(mol.K)。表明,土壤对石油污染物的吸附是自发进行且为放热过程,温度升高吸附量减少,石油被吸附的过程中混乱度降低。     

改性花生壳对水中苯酚的吸附热力学与动力学研究

通过甲醛—硫酸混合液改性花生壳对苯酚的吸附试验,研究了改性花生壳吸附苯酚的最佳条件、吸附热力学和动力学特征。采用Langmuir和Freundlich等温线对平衡数据进行了线性拟合,结果表明,改性花生壳对苯酚的吸附平衡符合Freundlich等温方程。在294 K下,吸附焓变△H=-11.41 kJ/mol,自由能△G=-5.09 kJ/mol,熵变△S=-21.50 J/(mol.K),表明该吸附过程为自发进行的放热过程。其动力学行为更好地符合Lagergren准二级动力学模型。     

酸性条件下红壤表面Zn~(2+)-H~+反应动力学的能量特征

用自行设计的动力学装置研究了酸性条件下Zn在红壤表面的反应动力学能量特征.结果表明,酸性条件下,Zn吸附分为快反应和慢反应.用一级动力学方程拟合的Zn最大吸附量:pH5.5处理Zn的最大吸附量在289 K时为1.79 mmol·kg~(-1),在313 K时为2.62 mmol·kg~(-1);pH3.3处理Zn的最大吸附量在289 K时为0.12 mmol·kg~(-1),在313 K时为0.16 mmol·kg~(-1).即吸附量随酸度增加显著下降,随温度升高明显增加.用扩散速率常数计算的活化能(△E~*):pH5.5处理Zn的△E~*为9.05 kJ·mol~(-1),pH3.3处理Zn的△E~*为12.02 kJ·mol~(-1),随酸度的增加△E*增加,Zn扩散需克服的能障加大,Zn吸附量降低.△H值为正,温度升高可促进Zn的扩散;△S值均为负,说明吸附反应使体系有序度增加.原液pH为5.5时,流出液的pH急剧下降;pH4.3、pH3.8和pH3.3时流出液比流入液的pH高,是由于土壤的缓冲作用和土壤表面质子化;当溶液中H~+超过一定数量后,反应初期的H~+消耗是快反应过程,H~+对矿物的溶蚀成为速率控制步骤.     

类Fenton试剂处理苯酚废水的影响因素及动力学研究

采用一种类Fenton试剂法,即Fe3+和H2O2的组合代替Fe2+和H2O2的组合法,对氧化降解苯酚的影响因素及反应动力学进行研究。结果表明:当Fe3+、H2O2的加入量分别为1.3×10-3和1.3×10-2mol·L-1,且初始pH值约为4时,苯酚的降解率最大,几乎达到100%。同时分别用一级动力学、二级动力学及复合一级动力学方程对该条件下的反应进行拟合,复合一级动力学方程能最佳拟合相应的动力学过程,但2个平行反应的速率系数k1≈9.24k2,因此可近似认为是一级动力学过程。     

交联碱木质素--聚乙烯醇基钾镁缓释膜肥对钾、镁的缓释性能

为了提高工业碱木质素的利用率和扩大其应用范围,以工业碱木质素和聚乙烯醇(PVA)为原料、甲醛作为交 联剂、添加硫酸钾和硫酸镁制备交联碱木质素-聚乙烯醇基钾镁缓释膜肥。采用FTIR-ATR 方法测定缓释膜肥的化 学结构,并用淋溶实验检验缓释膜肥对钾、镁的缓释作用。结果表明:1)缓释膜肥在3 260 cm-1 左右的峰变小变宽, 1 332.57 cm-1 处吸收峰消失,1 145.51 ~983.52 cm-1 范围内吸收峰变大,说明碱木质素、聚乙烯醇经甲醛交联有化 学反应发生。2)与纯PVA 交联薄膜相比,碱木质素的加入不利于钾的缓释,而适量的碱木质素有利于镁的缓释, 碱木质素加入量可达20%。随着甲醛加入量的增大,钾累积释放率减小;适量甲醛有利于镁的缓释,但随着甲醛加 入量的增大,缓释膜肥对镁的缓释性能降低。对镁的缓释,甲醛的合适加入量为3.59%。缓释膜肥对钾的缓释主 要是分子结构的物理阻挡作用,而镁缓释除了物理阻挡作用还有木质素的螯合作用。3)对缓释膜肥的动力学试验 数据进行拟合,钾缓释的4 种模型拟合程度都很高,其中Higuchi 模型拟合程度最高,决定系数为0.994 1,说明钾缓 释行为遵循Fick 扩散。镁缓释模型中Ritger-Peppas 模型的拟合程度最高,决定系数为0.974 2,其缓释指数(0.5 n1.0)表明镁缓释行为是扩散和溶蚀综合作用的结果。      

Organic glasses with exceptional thermodynamic and kinetic stability

Vapor deposition has been used to create glassy materials with extraordinary thermodynamic and kinetic stability and high density. For glasses prepared from indomethacin or 1,3-bis-(1-naphthyl)-5-(2-naphthyl)benzene, stability is optimized when deposition occurs on substrates at a temperature of 50 K below the conventional glass transition temperature. We attribute the substantial improvement in thermodynamic and kinetic properties to enhanced mobility within a few nanometers of the glass surface during deposition. This technique provides an efficient means of producing glassy materials that are low on the energy landscape and could affect technologies such as amorphous pharmaceuticals.     

A Quantum State-Resolved Insertion Reaction: O((1)D) + H(2)(J = 0) --> OH((2) product operator product operator product operator, v, N) + H((2)S)

The O((1)D) + H(2) --> OH + H reaction, which proceeds mainly as an insertion reaction at a collisional energy of 1.3 kilocalories per mole, has been investigated with the high-resolution H atom Rydberg "tagging" time-of-flight technique and the quasiclassical trajectory (QCT) method. Quantum state-resolved differential cross sections were measured for this prototype reaction. Different rotationally-vibrationally excited OH products have markedly different angular distributions, whereas the total reaction products are roughly forward and backward symmetric. Theoretical results obtained from QCT calculations indicate that this reaction is dominated by the insertion mechanism, with a small contribution from the collinear abstraction mechanism through quantum tunneling.     

Buckminsterfullerane: the inside story

The stereoisomers of fully reduced buckminsterfullerene C(60)H(60) have been investigated with the molecular mechanics program MM3. Although it might be expected that chemical reduction would deliver all of the hydrogens to the outside, the symmetric structure produced in this way is predicted to be highly strained. Moving just one hydrogen to the inside is predicted to decrease the energy by 53 kilocalories (kcal) per mole. Putting additional hydrogens on the inside further lowers the predicted energy (depending on the steric relations between them). The miniimum energy isomer is predicted to have ten hydrogens inside with C(1) symmetry and to have an energy 400 kcal/mol less than that of the all-outside isomer. These results suggest that a process which could achieve isomerization would produce a mixture of isomers, most of which with ten hydrogens on the inside.     

Free energy and temperature dependence of electron transfer at the metal-electrolyte interface

The rate constant of the electron-transfer reaction between a gold electrode and an electroactive ferrocene group has been measured at a structurally well-defined metal-electrolyte interface at temperatures from 1 degrees to 47 degrees C and reaction free energies from -1.0 to +0.8 electron volts (eV). The ferrocene group was positioned a fixed distance from the gold surface by the self-assembly of a mixed thiol monolayer of (eta(5)C(5)H(5))Fe(eta(5)C(5)H(4))CO(2)(CH(2))(16)SH and CH(3)(CH(2))(15)SH. Rate constants from 1 per second (s(-1)) to 2 x 10(4) s(-1) in 1 molar HClO(4) are reasonably fit with a reorganization energy of 0.85 eV and a prefactor for electron tunneling of 7 x 10(4) s(-1) eV(-1). Such self-assembled monolayers can be used to systematically probe the dependence of electron-transfer rates on distance, medium, and spacer structure, and to provide an empirical basis for the construction of interfacial devices such as sensors and transducers that utilize macroscopically directional electron-transfer reactions.     

Observation of Feshbach resonances in the F + H2 --> HF + H reaction

Reaction resonances, or transiently stabilized transition-state structures, have proven highly challenging to capture experimentally. Here, we used the highly sensitive H atom Rydberg tagging time-of-flight method to conduct a crossed molecular beam scattering study of the F + H2 --> HF + H reaction with full quantum-state resolution. Pronounced forward-scattered HF products in the v' = 2 vibrational state were clearly observed at a collision energy of 0.52 kcal/mol; this was attributed to both the ground and the first excited Feshbach resonances trapped in the peculiar HF(v' = 3)-H' vibrationally adiabatic potential, with substantial enhancement by constructive interference between the two resonances.     

Interplane Tunneling Magnetoresistance in a Layered Manganite Crystal

The current-perpendicular-to-plane magnetoresistance (CPP-MR) has been investigated for the layered manganite, La2-2xSr1+2xMn2O7 (x = 0.3), which is composed of the ferromagnetic-metallic MnO2 bilayers separated by nonmagnetic insulating block layers. The CPP-MR is extremely large (10(4) percent at 50 kilo-oersted) at temperatures near above the three-dimensional ordering temperature (Tc approximately 90 kelvin) because of the field-induced coherent motion between planes of the spin-polarized electrons. Below Tc, the interplane magnetic domain boundary on the insulating block layer serves as the charge-transport barrier, but it can be removed by a low saturation field, which gives rise to the low-field tunneling MR as large as 240 percent.     

Dimer preparation that mimics the transition state for the adsorption of H2 on the Si(100)-2 x 1 surface

A chemically induced dimer configuration was prepared on the silicon (Si) (100) surface and was characterized by scanning tunneling microscopy (STM) and spectroscopy (STS). These prepared dimers, which are essentially untilted and differ both electronically and structurally from the dynamically tilting dimers normally found on this surface, are more reactive than normal dimers. For molecular hydrogen (H2) adsorption, the enhancement is about 10(9) at room temperature. There is no appreciable barrier for the H2 reaction at prepared sites, indicating the prepared configuration closely approximates the actual dimer structure in the transition state. This previously unknown ability to prepare specific surface configurations has important implications for understanding and controlling reaction dynamics on semiconductor surfaces.     

混合盐胁迫对鹰嘴豆种子萌发的影响

通过砂床培养试验,研究不同浓度混合盐胁迫对两个品种鹰嘴豆萌发的影响.结果表明,在混合盐胁迫下,A-1(白皮)在盐浓度0.01 mol/L时的发芽率及发芽势达峰值,分别较对照提高了14.6%,25.6%;88-1(红皮)在0.005 mol/L时的发芽率及发芽势达峰值,分别较对照提高了3.1%,6.9%.在低浓度盐分(0...     

From force fields to dynamics: classical and quantal paths

Reaction path methods provide a powerful tool for bridging the gap between electronic structure and chemical dynamics. Classical mechanical reaction paths may usually be understood in terms of the force field in the vicinity of a minimum energy path (MEP). When there is a significant component of hydrogenic motion along the MEP and a barrier much higher than the average energy of reactants, quantal tunneling paths must be considered, and these tend to be located on the corner-cutting side of the MEP. As the curvature of the MEP in mass-scaled coordinates is increased, the quantal reaction paths may deviate considerably from the classical ones, and the force field must be mapped out over a wider region, called the reaction swath. The required force fields may be represented by global or semiglobal analytic functions, or the dynamics may be computed "directly" from the electronic structure results without the intermediacy of potential energy functions. Applications to atom and diatom reactions in the gas phase and at gas-solid interfaces and to reactions of polyatomic molecules in the gas phase, in clusters, and in aqueous solution are discussed as examples.     

关于化学反应速度常数的探讨

反应速度的单位是摩·升－１·时间－１,大多数为ｍｏｌ·ｌ－１·ｓ－１或ｍｏｌ·ｌ－１·ｍｉｎ－１。速度常数ｋ的单位取决于反应的级数,例如一级反应,速度常数的单位为ｓ－１,二级反应速度常数的单位是ｌ·ｍｏｌ－１·ｓ－１。对于可逆反应,当反应达平衡时,正逆反应的速度相等,得到Ｋ＝ｋｆ／ｋｒ。如果正逆反应的反应级数不同,所得的平衡常数Ｋ就有量纲。由热力学数据计算所得的平衡常数是无量纲的。为使热力学平衡Ｋ与Ｋ＝ｋｆ／ｋｒ所得的Ｋ一致,速度常数的单位只能是ｍｏｌ·ｌ－１·ｓ－１或ｍｏｌ·ｌ－１·ｍｉｎ－１。