Measuring picosecond isomerization kinetics via broadband microwave spectroscopy

The rotational spectrum of a highly excited molecule is qualitatively different from its pure rotational spectrum and contains information about the intramolecular dynamics. We have developed a broadband Fourier transform microwave spectrometer that uses chirped-pulse excitation to measure a rotational spectrum in the 7.5- to 18.5-gigahertz range in a single shot and thereby reduces acquisition time sufficiently to couple molecular rotational spectroscopy with tunable laser excitation. After vibrationally exciting a single molecular conformation of cyclopropane carboxaldehyde above the barrier to C-C single-bond isomerization, we applied line-shape analysis of the dynamic rotational spectrum to reveal a product yield and picosecond reaction rate that were significantly different from statistical predictions. The technique should be widely applicable to dynamical studies of radical intermediates, molecular complexes, and conformationally flexible molecules with biological interest.     

Rotation and solvation of ammonium ion

From nitrogen-15 spin-lattice relaxation times and nuclear Overhauser enhancements, the rotational correlation time (c) for (15)NH(4)(+) was determined in a series of solvents. Values of (c) range from 0.46 to 20 picoseconds. The solvent dependence of (c) cannot be explained in terms of solvent polarity, molecular dipole moment, solvent basicity, solvent dielectric relaxation, or solvent viscosity. The rapid rotation and the variation with solvent can be accounted for by a model that involves hydrogen bonding of an NH proton to more than one solvent molecule in a disordered solvation environment.     

High harmonic generation from multiple orbitals in N2

Molecular electronic states energetically below the highest occupied molecular orbital (HOMO) should contribute to laser-driven high harmonic generation (HHG), but this behavior has not been observed previously. Our measurements of the HHG spectrum of N2 molecules aligned perpendicular to the laser polarization showed a maximum at the rotational half-revival. This feature indicates the influence of electrons occupying the orbital just below the N2 HOMO, referred to as the HOMO-1. Such observations of lower-lying orbitals are essential to understanding subfemtosecond/subangstrom electronic motion in laser-excited molecules.     

Orientational dielectric relaxation of collisionless molecules

The generation of the orientation component of the polarization of matter in an electric field has previously been thought to require interaction of molecules with their neighbors. It is demonstrated that, even in the absence of collisions between neighboring molecules, hot isolated polyatomic molecules can reorient in response to an external field, thereby giving rise to the orientation component of polarization. This reorientation occurs through the interaction of rotation with molecular vibrations, which provides a heat bath to establish thermal rotational equilibrium. This effect is demonstrated for o-difluorobenzene, o-dichlorobenzene, and p-chlorotoluene, with an inhomogeneous electric field used to deflect molecular beams of these molecules.     

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.     

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.     

Probing the solvent-assisted nucleation pathway in chemical self-assembly

Hierarchical self-assembly offers a powerful strategy for producing molecular nanostructures. Although widely used, the mechanistic details of self-assembly processes are poorly understood. We spectroscopically monitored a nucleation process in the self-assembly of p-conjugated molecules into helical supramolecular fibrillar structures. The data support a nucleation-growth pathway that gives rise to a remarkably high degree of cooperativity. Furthermore, we characterize a helical transition in the nucleating species before growth. The self-assembly process depends strongly on solvent structure, suggesting that an organized shell of solvent molecules plays an explicit role in rigidifying the aggregates and guiding them toward further assembly into bundles and/or gels.     

Reversible optical transcription of supramolecular chirality into molecular chirality

In nature, key molecular processes such as communication, replication, and enzyme catalysis all rely on a delicate balance between molecular and supramolecular chirality. Here we report the design, synthesis, and operation of a reversible, photoresponsive, self-assembling molecular system in which molecular and supramolecular chirality communicate. It shows exceptional stereoselectivity upon aggregation of the molecules during gel formation with the solvent. This chirality is locked by photochemical switching, a process that is subsequently used to induce an inverted chiral supramolecular assembly as revealed by circular dichroism spectroscopy. The optical switching between different chiral aggregated states and the interplay of molecular and supramolecular chirality offer attractive new prospects for the development of molecular memory systems and smart functional materials.     

Quantum gas of deeply bound ground state molecules

Molecular cooling techniques face the hurdle of dissipating translational as well as internal energy in the presence of a rich electronic, vibrational, and rotational energy spectrum. In our experiment, we create a translationally ultracold, dense quantum gas of molecules bound by more than 1000 wave numbers in the electronic ground state. Specifically, we stimulate with 80% efficiency, a two-photon transfer of molecules associated on a Feshbach resonance from a Bose-Einstein condensate of cesium atoms. In the process, the initial loose, long-range electrostatic bond of the Feshbach molecule is coherently transformed into a tight chemical bond. We demonstrate coherence of the transfer in a Ramsey-type experiment and show that the molecular sample is not heated during the transfer. Our results show that the preparation of a quantum gas of molecules in specific rovibrational states is possible and that the creation of a Bose-Einstein condensate of molecules in their rovibronic ground state is within reach.     

刺云实胶对魔芋葡甘聚糖分子链拓扑缠结的分析

将魔芋葡甘聚糖(KGM)与刺云实胶(TG)以一定的比例复配,通过旋转流变仪测定KGM-TG复配体系的相关流变特性,结合分子动力学和拓扑分析学研究KGM和TG分子的作用方式,探讨刺云实胶对魔芋葡甘聚糖分子链拓扑缠结的作用机理。结果表明,刺云实胶与KGM分子间存在协同增效作用,分子链间的主要作用是氢键作用力,刺云实胶的添加使得KGM分子链间的拓扑缠结强度与密度的增强,复配体系的力学性能得到加强。从分子作用本质上验证了刺云实胶与KGM之间流变性能的理化实验结果。     

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.     

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.     

荷叶黄酮高效提取工艺条件的优化

采用三元二次旋转正交组合设计进行试验,观察了提取液、质量浓度、时间、温度和荷叶与溶剂质量之比等5个单因素对荷叶总黄酮提取率的影响,建立了提取工艺参数间的数学模型,得出表面活性剂助提荷叶黄酮的最佳工艺条件:浸提温度74.8～76.5℃、浸提时间38～43 min、荷叶与溶剂质量之比1:25～1:28.     

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.     

Anatomy of the photodissociation region in the orion bar

Much of the interstellar gas resides in photodissociation regions whose chemistry and energy balance is controlled by the flux of far-ultraviolet radiation upon them. These photons can ionize and dissociate molecules and heat the gas through the photoelectric effect working on dust grains. These regions have been extensively modeled theoretically, but detailed observational studies are few. Mapping of the prominent Orion Bar photodissociation region at wavelengths corresponding to the carbon-hydrogen stretching mode of polycyclic aromatic hydrocarbons, the 1-0 S(1) line of molecular hydrogen, and the J = 1-0 rotational line of carbon monoxide allows the penetration of the far-ultraviolet radiation into the cloud to be traced. The results strongly support the theoretical models and show conclusively that the incident far-ultraviolet radiation field, not shocks as has sometimes been proposed, is responsible for the emission in the Orion Bar.     

Dynamics of Carbonium Ions Solvated by Molecular Hydrogen: CH5+(H2)n (n = 1, 2, 3)

The dynamics of the carbonium ion (CH(5)(+)), a highly reactive intermediate with no equilibrium structure, was studied by measuring the infrared spectra for internally cold CH(5)(+)(H(2))n(n = 1, 2, 3) stored in an ion trap. First-principle molecular dynamics methods were used to directly simulate the internal motion for these ionic complexes. The combined experimental and theoretical efforts substantiated the anticipated scrambling motion in the CH(5)(+) core and revealed the effect of the solvent molecular hydrogen in slowing down the scrambling. The results indicate the feasibility of using solvent molecules to stabilize the floppy CH(5)(+) ion in order to make it amenable to spectroscopic study.     

玫瑰茄多酚提取条件的优化研究

运用二次回归正交旋转组合设计方法研究了温度、时问、液料比、乙醇浓度时玫瑰茄干花萼多酚提取率的影响,确定了多酚较优提取范围.结果表明.通过贡献率法计算出在试验范围内各因子对多酚提取率作用的大小依次为乙醇浓度＞提取时间＞提取温度＞液料比.用频率分析法得到多酚提取率高于1.01%的优化条件是:温度71.82～75.56℃,时间1.508～1.704 5 h,液料比26.095～27.645倍,乙醇浓度44.24%～51.12%,提取率是1.22%.     

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.     

Osmotic mechanism and negative pressure

When solute molecules are confined, they exert a positive pressure on the barrier. If this is simply the free solvent surface, balance of forces requires the solvent to attain an equal negative hydrostatic pressure. This offers a sufficient explanation for the reduction of the vapor pressure over a solution.     

Molecular recognition at crystal interfaces

Nucleation, growth, and dissolution of crystals have been studied by stereochemical approach involving molecular recognition at interfaces. A methodology is described for using ;;tailor-made' additives designed to interact stereospecifically with crystal surfaces during growth and dissolution. This procedure was instrumental in controlling crystal morphology and in revising the concept of the structure and symmetry of solid solutions. Consequently, it was applied to the transformation of centrosymmetric single crystals into solid solutions with polar arrangement displaying second-harmonic generation and to the performance of asymmetric synthesis of guest molecules inside centrosymmetric host crystals. The method has led to a discovery of a new ;;relay' mechanism explaining the effect of solvent on crystal growth. Finally, it allowed for the design of auxiliary molecules that act as promoters or inhibitors of crystal nucleation that can be used to resolve enantiomers and crystallize desired polymorphs.