Spontaneous emission spectrum in double quantum dot devices

A double quantum dot device is a tunable two-level system for electronic energy states. A dc electron current was used to directly measure the rates for elastic and inelastic transitions between the two levels. For inelastic transitions, energy is exchanged with bosonic degrees of freedom in the environment. The inelastic transition rates are well described by the Einstein coefficients, relating absorption with stimulated and spontaneous emission. The most effectively coupled bosons in the specific environment of the semiconductor device used here were acoustic phonons. The experiments demonstrate the importance of vacuum fluctuations in the environment for quantum dot devices and potential design constraints for their use for preparing long-lived quantum states.     

Vibrational promotion of electron transfer

By using laser methods to prepare specific quantum states of gas-phase nitric oxide molecules, we examined the role of vibrational motion in electron transfer to a molecule from a metal surface free from the complicating influence of solvation effects. The signature of the electron transfer process is a highly efficient multiquantum vibrational relaxation event, where the nitrogen oxide loses hundreds of kilojoules per mole of energy on a subpicosecond time scale. These results cannot be explained simply on the basis of Franck-Condon factors. The large-amplitude vibrational motion associated with molecules in high vibrational states strongly modulates the energetic driving force of the electron transfer reaction. These results show the importance of molecular vibration in promoting electron transfer reactions, a class of chemistry important to molecular electronics devices, solar energy conversion, and many biological processes.     

Coherent control of decoherence

Manipulation of quantum interference requires that the system under control remains coherent, avoiding (or at least postponing) the phase randomization that can ensue from coupling to an uncontrolled environment. We show that closed-loop coherent control can be used to mitigate the rate of quantum dephasing in a gas-phase ensemble of potassium dimers (K2), which acts as a model system for testing the general concepts of controlling decoherence. Specifically, we adaptively shaped the light pulse used to prepare a vibrational wave packet in electronically excited K2, with the amplitude of quantum beats in the fluorescence signal used as an easily measured surrogate for the purpose of optimizing coherence. The optimal pulse increased the beat amplitude from below the noise level to well above it, and thereby increased the coherence life time as compared with the beats produced by a transform-limited pulse. Closed-loop methods can thus effectively identify states that are robust against dephasing without any previous information about the system-environment interaction.     

Femtosecond dynamics of electron localization at interfaces

The dynamics of two-dimensional small-polaron formation at ultrathin alkane layers on a silver(111) surface have been studied with femtosecond time- and angle-resolved two-photon photoemission spectroscopy. Optical excitation creates interfacial electrons in quasi-free states for motion parallel to the interface. These initially delocalized electrons self-trap as small polarons in a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal within picoseconds by tunneling through the adlayer potential barrier. The energy dependence of the self-trapping rate has been measured and modeled with a theory analogous to electron transfer theory. This analysis determines the inter- and intramolecular vibrational modes of the overlayer responsible for self-trapping as well as the relaxation energy of the overlayer molecular lattice. These results for a model interface contribute to the fundamental picture of electron behavior in weakly bonded solids and can lead to better understanding of carrier dynamics in many different systems, including organic light-emitting diodes.     

Interception of excited vibrational quantum states by O2 in atmospheric association reactions

Bimolecular reactions in Earth's atmosphere are generally assumed to proceed between reactants whose internal quantum states are fully thermally relaxed. Here, we highlight a dramatic role for vibrationally excited bimolecular reactants in the oxidation of acetylene. The reaction proceeds by preliminary adduct formation between the alkyne and OH radical, with subsequent O(2) addition. Using a detailed theoretical model, we show that the product-branching ratio is determined by the excited vibrational quantum-state distribution of the adduct at the moment it reacts with O(2). Experimentally, we found that under the simulated atmospheric conditions O(2) intercepts ~25% of the excited adducts before their vibrational quantum states have fully relaxed. Analogous interception of excited-state radicals by O(2) is likely common to a range of atmospheric reactions that proceed through peroxy complexes.     

First-principles theory for the H + H2O, D2O reactions

A full quantum dynamical study of the reactions of a hydrogen atom with water, on an accurate ab initio potential energy surface, is reported. The theoretical results are compared with available experimental data for the exchange and abstraction reactions in H + D2O and H + H2O. Clear agreement between theory and experiment is revealed for available thermal rate coefficients and the effects of vibrational excitation of the reactants. The excellent agreement between experiment and theory on integral cross sections for the exchange reaction is unprecedented beyond atom-diatom reactions. However, the experimental cross sections for abstraction are larger than the theoretical values by more than a factor of 10. Further experiments are required to resolve this.     

Video-rate molecular imaging in vivo with stimulated Raman scattering

Optical imaging in vivo with molecular specificity is important in biomedicine because of its high spatial resolution and sensitivity compared with magnetic resonance imaging. Stimulated Raman scattering (SRS) microscopy allows highly sensitive optical imaging based on vibrational spectroscopy without adding toxic or perturbative labels. However, SRS imaging in living animals and humans has not been feasible because light cannot be collected through thick tissues, and motion-blur arises from slow imaging based on backscattered light. In this work, we enable in vivo SRS imaging by substantially enhancing the collection of the backscattered signal and increasing the imaging speed by three orders of magnitude to video rate. This approach allows label-free in vivo imaging of water, lipid, and protein in skin and mapping of penetration pathways of topically applied drugs in mice and humans.     

Strange and unconventional isotope effects in ozone formation

The puzzling mass-independent isotopic enrichment in ozone formation contrasts markedly with the more recently observed large unconventional mass-dependent ratios of the individual ozone formation rate constants in certain systems. An RRKM (Rice, Ramsperger, Kassel, Marcus)-based theory is used to treat both effects. Restrictions of symmetry on how energy is shared among the rotational/vibrational states of the ozone isotopomer, together with an analysis of the competition between the transition states of its two exit channels, permit the calculation of isotope effects consistent with a wide array of experimental results.     

State-to-State Rates for the D + H2(v = 1, j = 1) rarr HD(v', j') + H Reaction: Predictions and Measurements

A fully quantal wavepacket approach to reactive scattering in which the best available H(3) potential energy surface was used enabled a comparison with experimentally determined rates for the D + H(2)(v = 1, j = 1) --> HD(v' = 0, 1, 2; j') + H reaction at significantly higher total energies (1.4 to 2.25 electron volts) than previously possible. The theoretical results are obtained over a sufficient range of conditions that a detailed simulation of the experiment was possible, thus making this a definitive comparison of experiment and theory. Good to excellent agreement is found for the vibrational branching ratios and for the rotational distributions within each product vibrational level. However, the calculated rotational distributions are slightly hotter than the experimentally measured ones. This small discrepancy is more marked for products for which a larger fraction of the total energy appears in translation. The most likely explanation for this behavior is that refinements are needed in the potential energy surface.     

常用六种草坪草蒸散量及作物系数的研究

根据水分平衡法采用小型蒸渗仪测定了两种水分条件下 6种草坪草的蒸散量 ,并采用Penman Monteith经验公式计算确定了各草种的作物系数 .两种水分条件为充足供水和限量供水 .参试的草种为草地早熟禾 (PoapratensisL .Nuglade)、高羊茅 (FestucaarundinaceaSchreb .Hundog 5 )、多年生黑麦草 (LoliumperenneL .Advent)、普通狗牙根(Cynodondactylon(L .)Pers.)、野牛草 (Buchloedactyloides(Nutt.)Engelm .)、日本结缕草 (ZoysiajaponicaSteud .) .草种间 ,水分处理间的草坪蒸散量均表现较大差异 .充足供水的草坪的蒸散量比限量供水的蒸散量大 30 5～ 1 5 3 5mm .全生长季冷季型草坪草的蒸散量大于暖季型草坪草 ,最多相差 2 0 0mm .两种水分条件下 ,6种草坪草的生长季总蒸散量排序相同 ,最大蒸散量排序为高羊茅 (90 3 5 5mm) >草地早熟禾 (85 7 93mm) >多年生黑麦草 (85 0 91mm) >狗牙根 (82 5 6 1mm) >野牛草 (75 8 6 6mm) >日本结缕草 (70 1 5 5mm) .不同的水分处理 ,草种和季节对草坪的作物系数均有一定程度的影响 .冷季型草的生长季平均作物系数介于 0 98～ 1 0 9之间 ,暖季型草的介于 0 70～ 0 96之间 .充足供水条件下高羊茅和草地早熟禾的作物系数与限量供水条件下的作物系数差异不显著 ,多     

A Rotationally Resolved Fluorescence Excitation Spectrum of all-trans-1,4-Diphenyl-1,3-butadiene

Band 1 in the jet-cooled one-photon S(1) <-- S(0) fluorescence excitation spectrum of all-trans-1,4-diphenyl-1,3-butadiene has been rotationally resolved with a molecular beam laser spectrometer. Both the orientation of the optical transition moment and the rotational constants of the two vibronic levels have been measured. The molecule shows no evidence of being significantly distorted from a C(24) geometry when it is low in the vibrational manifolds of either of the two electronic states.     

Rate theories and puzzles of hemeprotein kinetics

The binding of dioxygen and carbon monoxide to heme proteins such as myoglobin and hemoglobin has been studied with flash photolysis. At temperatures below 200 K, binding occurs from within the heme pocket and, contrary to expectation, with nearly equal rates for both ligands. This observation has led to a reexamination of the theory of the association reaction taking into account friction, protein structure, and the nature of electronic transitions. The rate coefficients for the limiting cases of large and small friction are found with simple arguments that use characteristic lengths and times. The arguments indicate how transition state theory as well as calculations based on nonadiabatic perturbation theory, which is called the Golden Rule, may fail. For ligand-binding reactions the data suggest the existence of intermediate states not directly observed so far. The general considerations may also apply to other biomolecular processes such as electron transport.     

How do small water clusters bind an excess electron?

The arrangement of water molecules around a hydrated electron has eluded explanation for more than 40 years. Here we report sharp vibrational bands for small gas-phase water cluster anions, (H2O)(4-6)- and (D2O)(4-6)-. Analysis of these bands reveals a detailed picture of the diffuse electron-binding site. The electron is closely associated with a single water molecule attached to the supporting network through a double H-bond acceptor motif. The local OH stretching bands of this molecule are dramatically distorted in the pentamer and smaller clusters because the excited vibrational levels are strongly coupled to the electron continuum. The vibration-to-electronic energy transfer rates, as revealed by line shape analysis, are mode-specific and remarkably fast, with the symmetric stretching mode surviving for less than 10 vibrational periods [50 fs in (H2O)4-].     

紫色土丘陵区不同类型林地土壤呼吸特征

采用动态—密闭气室法(LI—6400—09)对紫色土丘陵区3种典型林地土壤呼吸速率进行了连续测定。结果表明:3种供试林地(柏树林、青冈林、桤木林)土壤呼吸速率呈明显的季节变化,并随地下5cm处土温呈相同趋势的多峰波动。青冈(Quercus glauca)、柏树(Cypresses funebris)、桤木(Alder cremastogyne)林地平均土壤呼吸速率分别为135.5、150.8、189.5mg·m-2·h-1,土壤呼吸速率呈桤木>柏树>青冈的趋势。土壤呼吸速率日变化随当日气温先升后降而表现为先增后减的趋势。温度是土壤呼吸的主要影响因子,3种林地(有枯枝落叶覆盖)土壤呼吸速率与地下5cm处土壤温度之间具有极显著的指数相关关系,R2分别为:R2柏树=0.6838;R2青冈=0.6645;R2桤=0.5982。柏树和桤木林地枯枝落叶的存在促进了林地土壤呼吸速率的增长,而青冈林地枯枝落叶对土壤呼吸有抑制作用,表现出一定的屏蔽作用,这种作用随着观测天数的增加而减弱。     

Determining transition-state geometries in liquids using 2D-IR

Many properties of chemical reactions are determined by the transition state connecting reactant and product, yet it is difficult to directly obtain any information about these short-lived structures in liquids. We show that two-dimensional infrared (2D-IR) spectroscopy can provide direct information about transition states by tracking the transformation of vibrational modes as a molecule crossed a transition state. We successfully monitored a simple chemical reaction, the fluxional rearrangement of Fe(CO)5, in which the exchange of axial and equatorial CO ligands causes an exchange of vibrational energy between the normal modes of the molecule. This energy transfer provides direct evidence regarding the time scale, transition state, and mechanism of the reaction.     

Direct measurement of the preferred sense of NO rotation after collision with argon

The preferred sense of product molecule rotation (clockwise or counterclockwise) in a bimolecular collision system has been measured. Rotationally inelastic collisions of nitric oxide (NO) molecules with Ar atoms were studied by combining crossed molecular beams, circularly polarized resonant multiphoton ionization probing, and velocity-mapped ion imaging detection. The observed sense of NO product rotation varies with deflection angle and is a strong function of the NO final rotational state. The largest preferences for sense of rotation are observed at the highest kinematically allowed product rotational states; for lower rotational states, the variation with deflection angle becomes oscillatory. Quantum calculations on the most recently reported NO-Ar potential give good agreement with the observed oscillation patterns in the sense of rotation.     

Black farmers/farms: The search for equity

Black farmers are still Black farmers, yet now are considered a part of minority or small or limited resource farmers/ranchers (SLRF/R) by the Department of Agriculture. Except for a few Southern states, their numbers have fallen from a remnant to a fragment in recent years. They continue to leave agriculture at a faster rate than whites. What few programs the Department has for this category of producers (SLRF/R) show genuine promise, provided they are pursued diligently by the Congress and the Department. Also vigorous enforcement of civil rights laws and directives of the Secretary and the new initiatives by the Office of Civil Rights Enforcement (OCRE) have to be sustained.     

用聚赖氨酸包被国产载玻片制作DNA芯片

用多聚赖氨酸对国产载玻片进行包被处理,在不同的固定条件下,比较其与进口多聚赖氨酸载玻片对大片段DNA和3′端氨基修饰寡核苷酸的固定效果.结果表明,在DNA固定率上,自行包被处理的国产载玻片与进口多聚赖氨酸载玻片没有显著差异;紫外交联对大片段DNA固定率影响显著,但对氨基修饰的寡核苷酸影响不显著;3种点样液中,进口点样液MSS点样效果最好,其次为3×SSC,第三是水.氨基修饰的寡核苷酸可以很好地固定在聚赖氨酸包被的载玻片上.     

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.     

汇率对跨国经营企业价值影响的实证分析

根据跨国经营企业价值／汇率弹性模型，得出了企业价值与汇率的函数关系；进一步，利用某些企业的实际数据，确定了这些企业价值与汇率关系式的系数，并预测了某企业未来价值的变化趋势。实证分析结果表明，跨国经营企业价值与汇率的相关性最高，其回归所得的函数具有较好的短期（一个季度内）预测效果，可以用于预测短期内跨国经营企业价值的变动。