(Amino)(aryl)carbenes: stable singlet carbenes featuring a spectator substituent

Several (amino)(aryl)carbenes have been shown to be stable at room temperature in solution and in the solid state. Electroneutrality of the carbene center is ensured by the amino group, which has both pi-donor and final sigma-acceptor electronic character. The aryl group remains a spectator substituent, as shown by single-crystal x-ray analysis and by its chemical behavior. Because only one electron-active substituent is needed, numerous stable carbenes will become accessible, which will open the way for new synthetic developments and applications in various fields.     

Detection and Characterization of the Cumulene Carbenes H2C5 and H2C6

Two cumulene carbenes, H2C5 and H2C6, were detected in a supersonic molecular beam by Fourier transform microwave spectroscopy. Their rotational and leading centrifugal distortion constants were determined with high accuracy, such that the entire radio spectrum can now be calculated. Like the known carbenes H2C3 and H2C4, both molecules have singlet electronic ground states and linear carbon-chain backbones. They can be produced in sufficiently high concentrations in the laboratory that their electronic spectra, expected to lie in the visible, should be readily detectable by laser spectroscopy. The microwave spectra of other, more exotic isomers may be detectable as well.     

Frontiers in surface scattering simulations

Theorists have recently made substantial progress in simulating reactive molecule-metal surface scattering but still face major challenges. The grand challenge is to develop an approach that enables accurate predictive calculations of reactions involving electronically excited states with potential curve crossings. This challenge is all the more daunting because collisions involving molecules heavier than H2 may be accompanied by substantial energy exchange with the surface vibrations (phonons), and because an electronic structure approach that allows molecule-surface interaction energies to be computed with chemical accuracy (1 kilocalorie per mole) is not yet available even for the electronic ground state of molecule-metal surface systems.     

Chemical cartography: finding the keys to the kinetic labyrinth

Very high resolution lasers allow spectroscopic pictures to be taken following a collision between two molecular reactants. The features of these "pictures" are the electronic, vibrational, rotational, and translational motions of the atomic particles, which relate the quantum states of the reactants to the quantum states of the products. Such state-to-state kinetic information can be used to test the shape and nature of the interaction potential that controls the collision process. The potential itself is akin to a map of the terrain through mountains and valleys where elevation is a measure of energy instead of height. Accurate mapping of this potential surface leads to an understanding of the forces which control rates and mechanisms of chemical reactions. The application of four different advanced laser techniques to the study of collisions between "hot" hydrogen(H) atoms and carbon dioxide(CO(2)) molecules has provided a wealth of information about both reactive and nonreactive collisions for this system. The availability of data for rotationally, vibrationally, and translationally inelastic excitation of CO(2) by H atoms, when compared with data for reactive events producing OH + CO, provides insights into the dynamics of collisions between H and CO(2), and illustrates the future promise of these powerful techniques for elucidating features of potential energy surfaces.     

Facile splitting of hydrogen and ammonia by nucleophilic activation at a single carbon center

In possessing a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble transition metal centers and thus could potentially mimic their chemical behavior. Although singlet di(amino)carbenes are inert toward dihydrogen, it is shown that more nucleophilic and electrophilic (alkyl)(amino)carbenes can activate H2 under mild conditions, a reaction that has long been known for transition metals. However, in contrast to transition metals that act as electrophiles toward dihydrogen, these carbenes primarily behave as nucleophiles, creating a hydride-like hydrogen, which then attacks the positively polarized carbon center. This nucleophilic behavior allows these carbenes to activate NH3 as well, a difficult task for transition metals because of the formation of Lewis acid-base adducts.     

Synthesis of Novel Thin-Film Materials by Pulsed Laser Deposition

Pulsed laser deposition (PLD) is a conceptually and experimentally simple yet highly versatile tool for thin-film and multilayer research. Its advantages for the film growth of oxides and other chemically complex materials include stoichiometric transfer, growth from an energetic beam, reactive deposition, and inherent simplicity for the growth of multilayered structures. With the use of PLD, artificially layered materials and metastable phases have been created and their properties varied by control of the layer thicknesses. In situ monitoring techniques have provided information about the role of energetic species in the formation of ultrahard phases and in the doping of semiconductors. Cluster-assembled nanocrystalline and composite films offer opportunities to control and produce new combinations of properties with PLD.     

Instrumental requirements for global atmospheric chemistry

The field of atmospheric chemistry is data-limited, primarily because of the challenge of measuring the key chemical constituents in the global environment. Several recent advances, however, in rugged, portable, remotesensing, ground-based instrumentation and accurate, fast-response airborne instrumentation have provided powerful tools for the understanding of stratospheric ozone, particularly in polar regions. Current discoveries of the role of heterogeneous chemical processes point to the need for better techniques for characterization of stratospheric aerosols. In the troposphere, advances in in situ, sensitive methods for detecting reactive nitrogen compounds have demonstrated the role that these compounds have in controlling global oxidation processes, but better measurements of the reservoir species by which the long-ranged transport of pollutant-reactive nitrogen compounds is thought to occur are urgently needed. The role of hydrocarbons, particularly those of natural origin, in ozone formation in rural areas has focused attention on the requirement for better speciation of these ubiquitous compounds. Lastly, rigorous instrument intercomparison experiments have provided unbiased estimates of measurement capabilities.     

Chemistry and chemical intermediates in supersonic free jet expansions

Short-lived intermediates often play key roles in determining the course of chemical reactions. Recently the combination of sophisticated laser techniques and supersonic free jet expansions has offered new insight into the structure and reactivity of such intermediates. Because of their extremely reactive nature the intermediates are produced in situ in the expansion. The free jet expansion provides cooling of the intermediates to very low temperatures, so that even complex organic free radicals and molecular ions can be identified and characterized. Radical-radical reactions and ionic cluster formation likewise proceed in the expansion and can be monitored by laser spectroscopy.     

Laser probing of chemical reaction dynamics

Lasers are used in increasingly sophisticated ways to carry out reactions between molecules in selected vibrational, rotational, and electronic states and to probe the product states of chemical reactions. Such investigations are providing unprecedented insights into chemical reaction dynamics, the study of the detailed motions that molecules undergo in simple chemical reactions. In many cases it is possible to describe the influence that specific types of molecular excitation have on reactive events. Experiments are also being carried out to leam about chemical reactivity as a function of the alignment of reagents. There is increasing excitement concerning the potential of laser methods to interrogate the transition states of molecular reactions.     

Conical intersection dynamics in NO2 probed by homodyne high-harmonic spectroscopy

Conical intersections play a crucial role in the chemistry of most polyatomic molecules, ranging from the simplest bimolecular reactions to the photostability of DNA. The real-time study of the associated electronic dynamics poses a major challenge to the latest techniques of ultrafast measurement. We show that high-harmonic spectroscopy reveals oscillations in the electronic character that occur in nitrogen dioxide when a photoexcited wave packet crosses a conical intersection. At longer delays, we observe the onset of statistical dissociation dynamics. The present results demonstrate that high-harmonic spectroscopy could become a powerful tool to highlight electronic dynamics occurring along nonadiabatic chemical reaction pathways.     

Synthesis of carbenes through substitution reactions at a carbene center

An (amino)(phosphino) carbene can be transformed into (amino)(phosphonio) carbenes, which undergo nucleophilic intermolecular as well as intramolecular substitution reactions at the carbene center. A variety of carbenes can be synthesized starting from a single carbene precursor. The resulting gamut of electronic and steric effects possible should open the way not only to a detailed study of the mechanism, but also to the subsequent improvement of catalytic reactions that involve carbene-transition metal complexes.     

Detection of trace molecular species using degenerate four-wave mixing

Spectroscopies that make use of laser light have provided an important tool to modern researchers for the nonintrusive analysis of chemical systems. The strengths and limitations of these spectroscopic techniques often determine the viability of scientific investigations. The unique properties of degenerate four-wave mixing, a nonlinear optical technique, have recently been found to provide powerful capabilities for a wide range of applications.     

Stable versions of transient push-pull carbenes: extending lifetimes from nanoseconds to weeks

A (phosphanyl)(trifluoromethyl)carbene is shown to be stable for weeks in solution at temperatures up to -30 degrees C. Its chemical behavior exactly matches that of its transient congeners, even to the extent that subtle effects, such as the recently discovered weak pi interaction with aromatics, are observed. The influence of substituents on the structure of push-pull carbenes is demonstrated by a single-crystal x-ray diffraction study of a (phosphanyl)[2, 6-bis(trifluoromethyl)phenyl]carbene. The lifetime of these molecules makes them accessible to a wider range of standard techniques, allowing their chemical and physical behaviors to be studied in more detail than was previously possible.     

Chemical waves

Spatial structures may occur in nonlinear systems far from equilibrium. Chemical waves, which are concentration variations of chemical species propagating in a system, are an example of such structures. A survey is given of some experiments on chemical waves by spectroscopic and microphotographic techniques, arranged according to different types of waves, different geometries, and various properties.     

Femtosecond clocking of the chemical bond

When a chemical bond is broken in a direct dissociation reaction, the process is so rapid that it has generally been considered instantaneous and thus unmeasurable. However, the bond does persist for times on the order of 10(-13) seconds after the photon has been absorbed. Femtosecond (10(-15) second) laser techniques can be used to directly clock this process, which describes the dynamics of the chemical bond. The time required to break the chemical bond in an elementary reaction has been measured and the characteristic repulsion length for the potential governing fragment separation has been obtained.     

The validity of the "diradical" hypothesis: direct femtoscond studies of the transition-state structures

Direct studies of diradicals, the molecular species hypothesized to be archetypal of chemical bond transformations in many classes of reactions, have been made using femtosecond laser techniques with mass spectrometry in a molecular beam. These studies are aimed at "freezing" the diradicals in time and in the course of the reaction. The passage of these species through the transition-state region was observed and the effect of total energy and alkyl substitution on the rates of bond closure and cleavage was examined. The results establish the nature of these intermediates and define their existence during reactions.     

树木物候簇群分析方法的应用研究

依据树木物候多个形态学特征的综合性质,应用数学分析模型对不同树木的物候期进行多元的数量化分类处理,找出树种生态物候类群间相似相异的亲缘关系,并从生态型学的角度划分出相应的树木生态对策物候表现型.     

利用反应挤出技术改善淀粉基聚合物性能的研究

淀粉基聚合物的开发利用很大程度地减轻了环境污染,具有广阔的应用前景。鉴于反应挤出技术在改变产品的结构和化学性质方面极具优势,综述了反应挤出技术在淀粉基接枝共聚物和纳米复合材料等多相复合体系中的发展应用。     

植物体内活性氧代谢及其信号传导

活性氧是植物体内一类化学性质很活泼、氧化能力很强的含氧物质的总称。它们能对机体细胞造成氧化损伤，但同时在各种防卫反应中起着积极的作用，概述了近年来植物体内活性氧代谢及其信号传导取得的研究成果。     

In situ studies of chemistry and structure of materials in reactive environments

Most materials and devices typically operate under specific environmental conditions, many of them highly reactive. Heterogeneous catalysts, for example, work under high pressure of reactants or in acidic solutions. The relationship between surface structure and composition of materials during operation and their chemical properties needs to be established in order to understand the mechanisms at work and to enable the design of new and better materials. Although studies of the structure, composition, chemical state, and phase transformation under working conditions are challenging, progress has been made in recent years in the development of new techniques that operate under a variety of realistic environments. With them, new chemistry and new structures of materials that are only present under reaction conditions have been uncovered.