Order-disorder transition in polycrystalline c60 films

High-resolution Raman spectroscopy of polycrystalline films of C(60) deposited under ultrahigh-vacuum conditions show that the spectrum below 244 +/- 3 kelvin consists of a superposition of two components whose relative contributions are temperature-dependent. The spectrum of the more intense of the two components is similar to that obtained for air- or oxygen-exposed samples of C(60) at room temperature, whereas the spectrum above 244 +/- 3 kelvin corresponds to one previously reported for oxygen-free samples of C(60). The results may indicate an order-disorder phase transition involving the percolation of a cluster of C(60) molecules engaged in coherent Raman scattering.     

Atomic memory for correlated photon states

We experimentally demonstrate emission of two quantum-mechanically correlated light pulses with a time delay that is coherently controlled via temporal storage of photonic states in an ensemble of rubidium atoms. The experiment is based on Raman scattering, which produces correlated pairs of spin-flipped atoms and photons, followed by coherent conversion of the atomic states into a different photon beam after a controllable delay. This resonant nonlinear optical process is a promising technique for potential applications in quantum communication.     

Raman spectroscopic evidence for two conformations of uncomplexed valinomycin in the solid state

Raman spectroscopy is applied for the first time to elucidate the different conformations of the carrier transport molecule, valinomycin. Splitting of the ester and amide carbonyl stretch vibrations is observed in the Raman spectrum of crystals of valinomycin grown from both n-octane and acetone. These observations support the contention that some ester carbonyl groups are intramolecularly hydrogen bonded. The Raman spectrum of valinomycin grown from o-dichlorobenzene does not display this feature.     

Evolution of magnetic and superconducting fluctuations with doping of high-Tc superconductors

Electronic Raman scattering from high- and low-energy excitations was studied as a function of temperature, extent of hole doping, and energy of the incident photons in Bi2Sr2CaCu2O8+/-delta superconductors. For underdoped superconductors, short-range antiferromagnetic (AF) correlations were found to persist with hole doping, and doped single holes were found to be incoherent in the AF environment. Above the superconducting (SC) transition temperature Tc, the system exhibited a sharp Raman resonance of B1g symmetry and energy of 75 millielectron-volts and a pseudogap for electron-hole excitations below 75 millielectron-volts, a manifestation of a partially coherent state forming from doped incoherent quasi particles. The occupancy of the coherent state increases with cooling until phase ordering at Tc produces a global SC state.     

Harnessing attosecond science in the quest for coherent X-rays

Modern laser technology has revolutionized the sensitivity and precision of spectroscopy by providing coherent light in a spectrum spanning the infrared, visible, and ultraviolet wavelength regimes. However, the generation of shorter-wavelength coherent pulses in the x-ray region has proven much more challenging. The recent emergence of high harmonic generation techniques opens the door to this possibility. Here we review the new science that is enabled by an ability to manipulate and control electrons on attosecond time scales, ranging from new tabletop sources of coherent x-rays to an ability to follow complex electron dynamics in molecules and materials. We also explore the implications of these advances for the future of molecular structural characterization schemes that currently rely so heavily on scattering from incoherent x-ray sources.     

玉米地微波相干和非相干散射模型比较分析(英文)

[目的]对玉米地微波相干和非相干散射模型进行比较分析。[方法]在Stile相干散射模型的基础上提出了针对玉米作物的相干散射模型,模型中使用物理光学(PO)和无限长介电圆柱体近似方法计算玉米叶片和秆的单散射体矩阵,替代了原模型中计算窄叶的单散射体模型,并在模型中考虑了不同散射机制之间相互作用所产生的相干分量。研究中所使用的非相干散射模型为密歇根森林散射模型(MIMICS)。使用吉林省公主岭地区玉米地部分生长周期内的实测数据为以上相干和非相干散射模型的输入参数,分别模拟L和C波段VV和HH极化的后向散射系数,并将这2个模型的模拟结果进行了比较。[结果]该模型在不考虑树干层的情况下,可应用于玉米地后向散射系数的模拟玉米;该相干散射模型在L波段的模拟结果较差,在植被生长初期表现为模拟结果没有明显的规律性;通过相干和非相干散射模型的比较分析,证实由散射机制引起的相干性是较小的。[结论]文中只分析了随入射角变化,相干和非相干散射模型的差异,在以后的研究中,需要进一步分析该差异随植被和土壤参数的变化情况。     

玉米地微波相干和非相干散射模型比较分析

[目的]对玉米地微波相干和非相干散射模型进行比较分析。[方法]在Stile相干散射模型的基础上提出了针对玉米作物的相干散射模型,模型中使用物理光学(PO)和无限长介电圆柱体近似方法计算玉米叶片和秆的单散射体矩阵,替代了原模型中计算窄叶的单散射体模型,并在模型中考虑了不同散射机制之间相互作用所产生的相干分量。研究中所使用的非相干散射模型为密歇根森林散射模型(MIMICS)。使用吉林省公主岭地区玉米地部分生长周期内的实测数据为以上相干和非相干散射模型的输入参数,分别模拟L和C波段VV和HH极化的后向散射系数,并将这2个模型的模拟结果进行了比较。[结果]该相干散射模型在L波段的模拟结果较差,在植被生长初期表现为模拟结果没有明显的规律性;通过相干和非相干散射模型的比较分析,证实由散射机制引起的相干性是较小的。[结论]文中只分析了随入射角变化,相干和非相干散射模型的差异,在以后的研究中,需要进一步分析该差异随植被和土壤参数的变化情况。     

Time-resolved investigation of coherently controlled electric currents at a metal surface

Studies of current dynamics in solids have been hindered by insufficiently brief trigger signals and electronic detection speeds. By combining a coherent control scheme with photoelectron spectroscopy, we generated and detected lateral electron currents at a metal surface on a femtosecond time scale with a contact-free experimental setup. We used coherent optical excitation at the light frequencies omega(a) and omega(a)/2 to induce the current, whose direction was controlled by the relative phase between the phase-locked laser excitation pulses. Time- and angle-resolved photoelectron spectroscopy afforded a direct image of the momentum distribution of the excited electrons as a function of time. For the first (n = 1) image-potential state of Cu(100), we found a decay time of 10 femtoseconds, attributable to electron scattering with steps and surface defects.     

Vacuum Squeezing of Solids: Macroscopic Quantum States Driven by Light Pulses

Femtosecond laser pulses and coherent two-phonon Raman scattering were used to excite KTaO3 into a squeezed state, nearly periodic in time, in which the variance of the atomic displacements dips below the standard quantum limit for half of a cycle. This nonclassical state involves a continuum of transverse acoustic modes that leads to oscillations in the refractive index associated with the frequency of a van Hove singularity in the phonon density of states.     

Advances in picosecond spectroscopy

Progress in the technology of picosecond spectroscopy in the past few years has made possible the generation of well-characterized pulses emitted by synchronously pumped tunable dye lasers. In addition, the development of sensitive emission and absorption detection methods and the advent of picosecond Raman and coherent anti-Stokes Raman spectroscopy make possible the direct observaton of picosecond transient spectra and lifetimes. The information obtained allows the complete determination of mechanisms through the identification of transient states, radicals, and ions that evolve during the course of a chemical or biological reaction.     

Spectroscopy using quantum logic

We present a general technique for precision spectroscopy of atoms that lack suitable transitions for efficient laser cooling, internal state preparation, and detection. In our implementation with trapped atomic ions, an auxiliary "logic" ion provides sympathetic laser cooling, state initialization, and detection for a simultaneously trapped "spectroscopy" ion. Detection is achieved by applying a mapping operation to each ion, which results in a coherent transfer of the spectroscopy ion's internal state onto the logic ion, where it is then measured with high efficiency. Experimental realization, by using 9Be+ as the logic ion and 27Al+ as the spectroscopy ion, indicates the feasibility of applying this technique to make accurate optical clocks based on single ions.     

X-ray-induced dissociation of H2O and formation of an O2-H2 alloy at high pressure

When subjected to high pressure and extensive x-radiation, water (H2O) molecules cleaved, forming O-O and H-H bonds. The oxygen (O) and hydrogen (H) framework in ice VII was converted into a molecular alloy of O2 and H2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrated that this crystalline solid differs from previously known phases. It remained stable with respect to variations in pressure, temperature, and further x-ray and laser exposure, thus opening new possibilities for studying molecular interactions in the hydrogen-oxygen binary system.     

Femtosecond resolution of soft mode dynamics in structural phase transitions

The microscopic pathway along which ions or molecules in a crystal move during a structural phase transition can often be described in terms of a collective vibrational mode of the lattice. In many cases, this mode, called a "soft" phonon mode because of its characteristically low frequency near the phase transition temperature, is difficult to characterize through conventional frequency-domain spectroscopies such as light or neutron scattering. A femtosecond time-domain analog of light-scattering spectroscopy called impulsive stimulated Raman scattering (ISRS) has been used to examine the soft modes of two perovskite ferroelectric crystals. The low-frequency lattice dynamics of KNbO(3) and BaTiO(3) are clarified in a manner that permits critical evaluation of microscopic models for their ferroelectric transitions. The results illustrate the advantages of ISRS over conventional Raman spectroscopy of low-frequency, heavily damped soft modes.     

Stimulated Raman scattering in hydrogen-filled hollow-core photonic crystal fiber

We report on stimulated Raman scattering in an approximately 1-meter-long hollow-core photonic crystal fiber filled with hydrogen gas under pressure. Light was guided and confined in the 15-micrometer-diameter hollow core by a two-dimensional photonic bandgap. Using a pulsed laser source (pulse duration, 6 nanoseconds; wavelength, 532 nanometers), the threshold for Stokes (longer wavelength) generation was observed at pulse energies as low as 800 +/- 200 nanojoules, followed by a coherent anti-Stokes (shorter wavelength) generation threshold at 3.4 +/- 0.7 microjoules. The pump-to-Stokes conversion efficiency was 30 +/- 3% at a pulse energy of only 4.5 microjoules. These energies are almost two orders of magnitude lower than any other reported energy, moving gas-based nonlinear optics to previously inaccessible parameter regimes of high intensity and long interaction length.     

Multiplex spectroscopy: determining the transition moments and absolute concentrations of molecular species

A procedure is described that uses two spectroscopic techniques, absorption and infrared degenerate four-wave mixing, in tandem (multiplex) to measure the transition dipole moments and absolute concentrations of molecular species in situ. The method is demonstrated by the measurement of the relative transition moments and concentrations of two dissimilar sample gas components, hydrogen chloride and nitrogen dioxide, but is applicable to a wide variety of molecules and, thus, can provide new information for transient molecular species. Further, difficulties in obtaining quantitative information through techniques such as laser-induced fluorescence, coherent anti-Stokes Raman scattering, and degenerate four-wave mixing spectroscopies can be overcome when a multiplex approach is used.     

Living cells as test tubes

The combination of specific probes and advanced optical microscopy now allows quantitative probing of biochemical reactions in living cells. On selected systems, one can detect and track a particular protein with single-molecule sensitivity, nanometer spatial precision, and millisecond time resolution. Metabolites, usually difficult to detect, can be imaged and monitored in living cells with coherent anti-Stokes Raman scattering microscopy. Here, we describe the application of these techniques in studying gene expression, active transport, and lipid metabolism.     

Probing nanoscale ferroelectricity by ultraviolet Raman spectroscopy

We demonstrated that ultraviolet Raman spectroscopy is an effective technique to measure the transition temperature (Tc) in ferroelectric ultrathin films and superlattices. We showed that one-unit-cell-thick BaTiO3 layers in BaTiO3/SrTiO3 superlattices are not only ferroelectric (with Tc as high as 250 kelvin) but also polarize the quantum paraelectric SrTiO3 layers adjacent to them. Tc was tuned by approximately 500 kelvin by varying the thicknesses of the BaTiO3 and SrTiO3 layers, revealing the essential roles of electrical and mechanical boundary conditions for nanoscale ferroelectricity.     

基于BiPLS-CARS-PLS的哈密瓜冠层叶片SPAD值反演建模

利用光谱技术对大田哈密瓜冠层叶片叶绿素含量定量估测,可为田间水肥调控以及田间管理提供理论依据。本实验在剔除噪音后的378 nm到1 115 nm光谱的基础上采用多元散射校正、标准正态变量相交、标准化、Savitzky-Golay卷积平滑法、归一化、移动平均平滑等方法对原始光谱数据进行预处理,然后采用特征区间选择与特征波长选择相结合的方法实现数据降维和简化模型,并建立偏最小二乘和极限学习机的回归模型。结果表明,多元散射校正预处理效果最佳,在此基础上,利用反向区间偏最小二乘法(BiPLS)和竞争性自适应重加权采样算法(CARS)相结合共筛选出13个特征波长,将其作为模型的输入变量,由偏最小二乘法(PLS)建立的模型效果最优,其预测集的相关系数R_p和均方根误差RMSEP分别为0.942 4与1.006 2。因此,采用BiPLS与 CARS结合PLS建立的光谱定量分析模型,可实现对哈密瓜冠层叶片叶绿素含量的定量估测。     

Measurement of the distribution of site enhancements in surface-enhanced Raman scattering

On nanotextured noble-metal surfaces, surface-enhanced Raman scattering (SERS) is observed, where Raman scattering is enhanced by a factor, G, that is frequently about one million, but underlying the factor G is a broad distribution of local enhancement factors, eta. We have measured this distribution for benzenethiolate molecules on a 330-nanometer silver-coated nanosphere lattice using incident light of wavelength 532 nanometers. A series of laser pulses with increasing electric fields burned away molecules at sites with progressively decreasing electromagnetic enhancement factors. The enhancement distribution P(eta)deta was found to be a power law proportional to (eta)(-1.75), with minimum and maximum values of 2.8 x 10(4) and 4.1 x 10(10), respectively. The hottest sites (eta >10(9)) account for just 63 in 1,000,000 of the total but contribute 24% to the overall SERS intensity.     

The spectroscopy of very cold gases

The technique of supersonic free jet spectroscopy can be used to study the structure and dynamics of molecules which have been cooled to far below their boiling points but which remain in the gas phase. Cooling of the internal degress of freedom, the molecular rotations and vibrations, produces a highly resolved and greatly simplified molecular spectrum. The principles of the technique are discussed and its utility is demonstrated by two examples. the spectroscopy of porphyrins in the gas phase and the photochemistry of van der Waals molecules.