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.     

Microwave spectrum and structure of sulfur difluoride

Sulfur difluioride has been identified and characterized from its microwave spectrum. The analysis of rotational transitions for both sulfur difluoride-32 and sulfur difluoride-34 shows that this molecular species has C(2v) symmetry with a bond length of 1.589 angstroms, a bond angle of 98 degrees 16', and a dipole moment of 1.05 Debye.     

Seemingly anomalous angular distributions in H + D₂ reactive scattering

When a hydrogen (H) atom approaches a deuterium (D(2)) molecule, the minimum-energy path is for the three nuclei to line up. Consequently, nearly collinear collisions cause HD reaction products to be backscattered with low rotational excitation, whereas more glancing collisions yield sideways-scattered HD products with higher rotational excitation. Here we report that measured cross sections for the H + D(2) → HD(v' = 4, j') + D reaction at a collision energy of 1.97 electron volts contradict this behavior. The anomalous angular distributions match closely fully quantum mechanical calculations, and for the most part quasiclassical trajectory calculations. As the energy available in product recoil is reduced, a rotational barrier to reaction cuts off contributions from glancing collisions, causing high-j' HD products to become backward scattered.     

Ultraviolet spectrometer observations of uranus

Data from solar and stellar occultations of Uranus indicate a temperature of about 750 kelvins in the upper levels of the atmosphere (composed mostly of atomic and molecular hydrogen) and define the distributions of methane and acetylene in the lower levels. The ultraviolet spectrum of the sunlit hemisphere is dominated by emissions from atomic and molecular hydrogen, which are kmown as electroglow emissions. The energy source for these emissions is unknown, but the spectrum implies excitation by low-energy electrons (modeled with a 3-electron-volt Maxwellian energy distribution). The major energy sink for the electrons is dissociation of molecular hydrogen, producing hydrogen atoms at a rate of 10(29) per second. Approximately half the atoms have energies higher than the escape energy. The high temperature of the atmosphere, the small size of Uranus, and the number density of hydrogen atoms in the thermosphere imply an extensive thermal hydrogen corona that reduces the orbital lifetime of ring particles and biases the size distribution toward larger particles. This corona is augmented by the nonthermal hydrogen atoms associated with the electroglow. An aurora near the magnetic pole in the dark hemisphere arises from excitation of molecular hydrogen at the level where its vertical column abundance is about 10(20) per square centimeter with input power comparable to that of the sunlit electroglow (approximately 2x10(11) watts). An initial estimate of the acetylene volume mixing ratio, as judged from measurements of the far ultraviolet albedo, is about 2 x 10(-7) at a vertical column abundance of molecular hydrogen of 10(23) per square centimeter (pressure, approximately 0.3 millibar). Carbon emissions from the Uranian atmosphere were also detected.     

Picometer-scale electronic control of molecular dynamics inside a single molecule

Tunneling electrons from a low-temperature (5 kelvin) scanning tunneling microscope were used to control, through resonant electronic excitation, the molecular dynamics of an individual biphenyl molecule adsorbed on a silicon(100) surface. Different reversible molecular movements were selectively activated by tuning the electron energy and by selecting precise locations for the excitation inside the molecule. Both the spatial selectivity and energy dependence of the electronic control are supported by spectroscopic measurements with the scanning tunneling microscope. These experiments demonstrate the feasibility of controlling the molecular dynamics of a single molecule through the localization of the electronic excitation inside the molecule.     

Real-time observation of molecular motion on a surface

The laser-induced movement of CO molecules over a platinum surface was followed in real time by means of ultrafast vibrational spectroscopy. Because the CO molecules bound on different surface sites exhibit different C-O stretch vibrational frequencies, the site-to-site hopping, triggered by excitation with a laser pulse, can be determined from subpicosecond changes in the vibrational spectra. The unexpectedly fast motion--characterized by a 500-femtosecond time constant--reveals that a rotational motion of the CO molecules, rather than pure translation, is required for this diffusion process. This conclusion is corroborated by density functional theory calculations.     

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.     

Molecular loops in the galactic center: evidence for magnetic flotation

The central few hundred parsecs of the Milky Way host a massive black hole and exhibit very violent gas motion and high temperatures in molecular gas. The origin of these properties has been a mystery for the past four decades. Wide-field imaging of the (12)CO (rotational quantum number J = 1 to 0) 2.6-millimeter spectrum has revealed huge loops of dense molecular gas with strong velocity dispersions in the galactic center. We present a magnetic flotation model to explain that the formation of the loops is due to magnetic buoyancy caused by the Parker instability. The model has the potential to offer a coherent explanation for the origin of the violent motion and extensive heating of the molecular gas in the galactic center.     

生防外生菌根真菌的筛选及其生长和发酵条件优化

为了筛选具有广谱拮抗活性的外生菌根真菌,采用平板对峙法(初筛)和生长速率法(复筛)测定了6种外生菌根真菌对5种常见植物病原真菌的抑制活性,通过单因素试验对抑制效果较好的生防菌进行生长及发酵条件优化。结果表明,彩色豆马勃Pt01在初筛试验中对植物病原真菌的抑菌率为40.1%~49.7%,在复筛试验中抑菌率为78.5%~91.8%,抑菌作用整体高于其他外生菌根真菌。条件优化后发现,Pt01在28℃、p H值为7.0、碳源为乳糖、氮源为硝酸钾时生长最好;其最佳发酵条件:温度为30℃,初始p H值为6.0,碳源为乳糖,氮源为酵母膏,时间为5 d,转速对不同病原真菌抑菌率各有不同影响,需要单独考虑最佳转速。彩色豆马勃菌株Pt01对5种受试病原真菌均有明显的抑制作用,优化其生长和发酵条件为其在植物病害防治上的应用提供了理论依据。     

Coherent optical control of the quantum state of a single quantum Dot

Picosecond optical excitation was used to coherently control the excitation in a single quantum dot on a time scale that is short compared with the time scale for loss of quantum coherence. The excitonic wave function was manipulated by controlling the optical phase of the two-pulse sequence through timing and polarization. Wave function engineering techniques, developed in atomic and molecular systems, were used to monitor and control a nonstationary quantum mechanical state composed of a superposition of eigenstates. The results extend the concept of coherent control in semiconductors to the limit of a single quantum system in a zero-dimensional quantum dot.     

Tunneling spectroscopy of the elementary excitations in a one-dimensional wire

The collective excitation spectrum of interacting electrons in one dimension has been measured by controlling the energy and momentum of electrons tunneling between two closely spaced, parallel quantum wires in a GaAs/AlGaAs heterostructure while measuring the resulting conductance. The excitation spectrum deviates from the noninteracting spectrum, attesting to the importance of Coulomb interactions. An observed 30% enhancement of the excitation velocity relative to noninteracting electrons with the same density, a parameter determined experimentally, is consistent with theories on interacting electrons in one dimension. In short wires, 6 and 2 micrometers long, finite size effects, resulting from the breaking of translational invariance, are observed.     

CRASY: mass- or electron-correlated rotational alignment spectroscopy

Rotational spectra have traditionally been measured without a concurrent means of differentiating the molecular constituents of the sample. Here, we present an all-optical multipulse experiment that allows the correlated measurement of rotational and mass or photoelectron spectra by combining Fourier transform rotational coherence spectroscopy with resonance-enhanced multiphoton ionization. We demonstrate the power of this method with the determination of ground-state rotational constants and fragmentation channels for 10 different isotopes in a natural carbon disulfide sample. Three of the reported rotational constants were previously inaccessible by conventional spectroscopic techniques.     

Multiple-quantum nuclear magnetic resonance spectroscopy

A nuclear magnetic resonance (NMR) event is popularly viewed as the flip of a single spin in a magnetc field, stimulated by the absorption or emission of only one quantum of radio-frequency energy. Nevertheless, resonances between nuclear spin states that differ by more than one unit in the Zeeman quantum number also can be induced in systems of coupled spins by suitably designed sequences of radio-frequency pulses. Pairs of states excited in this way oscillate coherently at the frequencies of the corresponding multiple-quantum transitions and produce a response that may be monitored indirectly in a two-dimensional time-domain experiment. The pattern of multiple-quantum excitation and response, influenced largely by the concerted interactions of groups of coupled nuclei, simplifies the NMR spectrum in some instances and provides significant new information in others. Applications of multiple-quantum NMR extend to problems in many different areas, ranging from studies of the structure and function of proteins and nucleic acids in solution to investigations of the arrangements of atoms in amorphous semiconductors. The specific spectroscopic techniques are varied as well and include methods designed, for example, to simplify spectral analysis for liquids and liquid crystals, eliminate inhomogeneous broadening, study interatomic connectivity in liquid-state molecules, identify clusters of atoms in solids, enhance the spatial resolution in solid-state imaging experiments, and probe correlated molecular motions.     

Homogeneous Linewidths in the Optical Spectrum of a Single Gallium Arsenide Quantum Dot

The homogeneous linewidths in the photoluminescence excitation spectrum of a single, naturally formed gallium arsenide (GaAs) quantum dot have been measured with high spatial and spectral resolution. The energies and linewidths of the homogeneous spectrum provide a new perspective on the dephasing dynamics of the exciton in a quantum-confined, solid-state system. The origins of the linewidths are discussed in terms of the dynamics of the exciton in zero dimensions, in particular, in terms of lifetime broadening through the emission or absorption of phonons and photons.     

Roton-type mode softening in a quantum gas with cavity-mediated long-range interactions

Long-range interactions in quantum gases are predicted to give rise to an excitation spectrum of roton character, similar to that observed in superfluid helium. We investigated the excitation spectrum of a Bose-Einstein condensate with cavity-mediated long-range interactions, which couple all particles to each other. Increasing the strength of the interaction leads to a softening of an excitation mode at a finite momentum, preceding a superfluid-to-supersolid phase transition. We used a variant of Bragg spectroscopy to study the mode softening across the phase transition. The measured spectrum was in very good agreement with ab initio calculations and, at the phase transition, a diverging susceptibility was observed. The work paves the way toward quantum simulation of long-range interacting many-body systems.     

Signatures of H2CO photodissociation from two electronic states

Even in small molecules, the influence of electronic state on rotational and vibrational product energies is not well understood. Here, we use experiments and theory to address this issue in photodissociation of formaldehyde, H2CO, to the radical products H + HCO. These products result from dissociation from the singlet ground electronic state or the first excited triplet state (T1) of H2CO. Fluorescence spectra reveal a sudden decrease in the HCO rotational energy with increasing photolysis energy accompanied by substantial HCO vibrational excitation. Calculations of the rotational distribution using an ab initio potential energy surface for the T1 state are in very good agreement with experiment and strongly support dominance of the T1 state in the dynamics at the higher photolysis energies.     

Microwave detection of thioformaldehyde

Thioformaldehyde (H(2)CS) has been detected and characterized from its microwave spectrum. Preliminary analysis of rotational transitions for the sulfur-32-containing form of H(2)CS shows this new species to have C(2v) symmetry with rotational constants (in megahertz) of A = 292,729, B = 17,698, and C = 16,652. The possibility of detection of thioformaldehyde in the interstellar medium is discussed, and a table of transitions expected to be of importance for that detection is presented.     

Alterations of single molecule fluorescence lifetimes in near-field optical microscopy

Fluorescence lifetimes of single Rhodamine 6G molecules on silica surfaces were measured with pulsed laser excitation, time-correlated single photon counting, and near-field scanning optical microscopy (NSOM). The fluorescence lifetime varies with the position of a molecule relative to a near-field probe. Qualitative features of lifetime decreases are consistent with molecular excited state quenching effects near metal surfaces. The technique of NSOM provides a means of altering the environment of a single fluorescent molecule and its decay kinetics in a repeatable fashion.     

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.     

Understanding the infrared spectrum of bare CH5+

Protonated methane, CH5+, continues to elude definitive structural assignment, as large-amplitude vibrations and hydrogen scrambling challenge both theory and experiment. Here, the infrared spectrum of bare CH5+ is presented, as detected by reaction with carbon dioxide gas after resonant excitation by the free electron laser at the FELIX facility in the Netherlands. Comparison of the experimental spectrum at approximately 110 kelvin to finite-temperature infrared spectra, calculated by ab initio molecular dynamics, supports fluxionality of bare CH5+ under experimental conditions and provides a dynamical mechanism for exchange of hydrogens between CH3 tripod positions and the three-center bonded H2 moiety, which eventually leads to full hydrogen scrambling. The possibility of artificially freezing out scrambling and internal rotation in the simulations allowed assignment of the infrared spectrum despite this pronounced fluxionality.