Shedding light on a dark state: the energetically lowest quintet state of C2

In this work we present a deperturbation study of the d?(3)Π(g), v=6 state of C(2) by double-resonant four-wave mixing spectroscopy. Accurate line positions of perturbed transitions are unambiguously assigned by intermediate level labeling. In addition, extra lines are accessible by taking advantage of the sensitivity and high dynamic range of the technique. These weak spectral features originate from nearby-lying dark states that gain transition strength through the perturbation process. The deperturbation analysis of the complex spectral region in the (6,5) and (6,4) bands of the Swan system (d(3)Π(g)-a?(3)Π(u)) unveils the presence of the energetically lowest high-spin state of C(2) in the vicinity of the d?(3)Π(g), v=6 state. The term energy curves of the three spin components of the d state cross the five terms of the 1?(5)Π(g) state at rotational quantum numbers N ≤ 11. The spectral complexity for transitions to the v = 6 level of d?(3)Π(g) state is further enhanced by an additional perturbation at N = 19 and 21 owing to the b?(3)Σ(g)(-), v=19 state. The spectroscopic characterization of both dark states is accessible by the measurement of 122 "window" levels. A global fit of the positions to a conventional Hamiltonian for a linear diatomic molecule yields accurate molecular constants for the quintet and triplet perturber states for the first time. In addition, parameters for the spin-orbit and L-uncoupling interaction between the electronic levels are determined. The detailed deperturbation study unravels major issues of the so-called high-pressure bands of C(2). The anomalous nonthermal emission initially observed by Fowler in 1910 [Mon. Not. R. Astron. Soc. 70, 484 (1910)] and later observed in numerous experimental environments are rationalized by taking into account "gateway" states, i.e., rotational levels of the d?(3)Π(g), v=6 state that exhibit significant (5)Π(g) character through which all population flows from one electronic state to the other.     

Conformational transitions of glycine induced by vibrational excitation of the O-H stretch

Vibrational energy flow and conformational transitions following excitation of the OH stretching mode of the most stable conformer of glycine are studied by classical trajectories. "On the fly" simulations with the PM3 semiempirical electronic structure method for the potential surface are used. Initial conditions are selected to correspond to the ν=1 excitation of the OH stretch. The main findings are: (1) An an equilibrium-like ratio is established between the populations of the 3 lowest-lying conformers after about 10 picoseconds. (2) There is a high probability throughout the 150 ps of the simulations for finding the molecule in geometries far from the equilibrium structures of the lowest-energy conformers. (3) Energy from the initial excited OH (ν=1) stretch flows preferentially to 5 other vibrational modes, including the bending motion of the H atom. (4) RRK theory yields conformational transition rates that deviate substantially from the classical trajectory results. Possible implication of these results for vibrational energy flow and conformational transitions in small biological molecules are discussed.     

From Y- to Siamese-twin shaped glycolipids

Summary A set of Y-shaped and Siamese-twin shaped carbohydrate based glycolipids was investigated using polarising microscopy. The structure was changed from the normal type (1 head, two chains) to complex inverted structures (2 heads outside 1 to 3 chains in the middle part). The carbohydrate headgroup was changed from mono- to disaccharide; also the alkyl chain length was varied systematically. The compounds displayed different thermotropic mesophases (Smectic A phases, columnar phases and cubic phases) depending on the type of carbohydrate headgroup and the alkyl chain length.     

Attenuations and atomic spin precessions of γ-angular correlations for coulomb excited19F nuclei in single-electron ions

Attenuated γ-angular correlations and atomic spin precessions were measured for single-electron fluorine ions recoiling through vacuum in weak transverse magnetic fields The Coulomb excited long-lived¹⁹F(5/2⁺) state at 197 keV was used as probe. The angular correlations observed in the focal coordinate system of the Coulomb excitation process as well as the spin precessions in weak external fields are well explained with simple electron configurations associated with the highly stripped ions.     

CFD-based predictive control of melt temperature in plastic injection molding

A unique method of coupling computational fluid dynamics (CFD) to model predictive control (MPC) for controlling melt temperature in plastic injection molding is presented. The methodology is based on using CFD to generate, via open-loop testing, a temperature and input dependent system model for multi-variable control of a three-heater barrel on an injection molding machine. Results clearly show the benefit of temperature and input dependent system models for MPC control, and that CFD can be used to dramatically reduce the time associated with open-loop testing through physical experiments.     

Rapid communicationPhotoelectron emission in femtosecond laser assisted scanning tunneling microscopy

Direct illumination of the tunneling gap in an ultrahigh vacuum scanning tunneling microscope with ultrashort pump-probe laser pulses may offer ultimate spatial and temporal resolution in surface experiments. The electronic bandwidth of the tunneling gap ( 1 THz) does not limit the time resolution. Our experiments show that multiphoton photoelectron emission from the sample limits the application of this detection scheme at high laser fluence. However, a substrate specific pump-probe effect in the photoelectron yield with femtosecond transients is observed on Tantalum and on GaAs(110) surfaces. Received: 5 November 1996     

Controlling the spectral shape of coherent soft X-rays

We demonstrate the generation of arbitrarily shaped spectra of coherent soft X-ray radiation by adaptive control of the driving laser pulse. The selection of both narrow and wide spectral ranges as well as suppression of high-harmonic emission in a selected wavelength region is achieved. Feedback-controlled spectral engineering of coherent soft X-rays paves the way to shaping of soft X-ray pulses and coherent control of electron dynamics in the sub-femtosecond regime.     

Transient field measurements on light and heavy ions in amorphous iron-boron compounds

Measurements of transient magnetic fields (TF) were performed for the first time in the amorphous compounds of Fe₈₀B₂₀ and Fe₈₅B₁₅ for ²⁴Mg(2⁺), ²⁸Si(2⁺), ⁴⁸Ti(2⁺) and ⁵⁶Fe(2⁺) probe ions employing light and heavy ion beams. The motivation for these experiments was to investigate whether ion beam induced attenuations of TF are substantially weaker in these materials than in crystalline Fe. This expectation was indeed satisfied. The attenuations observed were found to be smaller at least by a factor of 2.     

Reorganization of the structures,morphologies, and conformations of bulk polymers via coalescence from polymer–cyclodextrin inclusion compounds

Bulk poly(ethylene terephthalate) (PET) and bisphenol A polycarbonate (PC) samples have been produced by the coalescence of their segregated, extended chains from the narrow channels of the crystalline inclusion compounds (ICs) formed between the γ‐cyclodextrin (CD) host and PET and PC guests, which are reported for the first time. Differential scanning calorimetry, Fourier transform infrared, and X‐ray observations of PET and PC samples coalesced from their crystalline γ‐CD‐ICs suggest structures and morphologies that are different from those of samples obtained by ordinary solution and melt processing techniques. For example, as‐received PC is generally amorphous with a glass‐transition temperature (T_g) of about 150 °C; when cast from tetrahydrofuran solutions, PC is semicrystalline with a melting temperature (T_m) of about 230 °C; and after PC/γ‐CD‐IC is washed with hot water for the removal of the host γ‐CD and for the coalescence of the guest PC chains, it is semicrystalline but has an elevated T_m value of about 245 °C. PC crystals formed upon the coalescence of highly extended and segregated PC chains from the narrow channels in the γ‐CD host lattice are possibly more chain‐extended and certainly more stable than chain‐folded PC crystals grown from solution. Melting the PC crystals formed by coalescence from PC/γ‐CD‐IC produces a normal amorphous PC melt that, upon cooling, results in typical glassy PC. PET coalesced from its γ‐CD‐IC crystals, although also semicrystalline, displays a T_m value only marginally elevated from that of typical bulk or solution‐crystallized PET samples. However, after the melting of γ‐CD‐IC‐coalesced PET crystals, it is difficult to quench the resultant PET melt into the usual amorphous PET glass, characterized by a T_g value of about 80 °C. Instead, the coalesced PET melt rapidly recrystallizes during the attempted quench, and so upon reheating, it displays neither a T_g nor a crystallization exotherm but simply remelts at the as‐coalesced T_m. This behavior is unaffected by the coalesced PET sample being held above T_m for 2 h, indicating that the extended, unentangled nature of the chains in the noncrystalline regions of the coalesced PET are not easily converted into the completely disordered, randomly coiled, entangled melt. Apparently, the highly extended, unentangled characters of the PC and PET chains in their γ‐CD‐ICs are at least partially retained after they are coalesced. Initial differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared, and X‐ray observations are described here. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 992–1012, 2002     

Cross sections of the interactions of He nuclei with protons

⁴He-p collisions at two values of⁴He momenta 8.6 GeV/c and 13.6 GeV/c as well as the³He-p collisions at 13.5 GeV/c have been studies using the one-meter JINR hydrogen bubble chamber. Total, elastic, topological and reaction cross sections have been measured. The cross sections have been determined on a sample of minimum biased events.