Thermodynamic properties of solid naphthalene: Cell model and quasiharmonic calculations

Cell model and quasihannonic calculations have been made for solid naphthalene, using the atom-atom approximation for intermolecular interactions. Throughout the temperature range examined (78–323 K) the cell model is found to be superior to the quasiharmonic approximation in describing the basic thermodynamic functions of the crystal. An attempt is also made to extend the cell model to calculate the elasticity tensor and thermal expansion.     

1-羟基-5-十二烷氧基-萘LB膜结构和取向的光谱研究

用红外透射,反射光谱及紫外可见吸收光谱方法研究了１－羟基－５－十二烷基－萘ＬＢ膜及溶液状态下的结构,分子取向。研究结果表明分子在溶液中主要是以单体形式存在;在ＬＢ膜中是以聚集体形式存在。     

Synergistic effects in toluene/C3H4 isomers co-pyrolysis: Formation of indene and naphthalene

A combination of experimental and kinetic modeling study is performed to explore synergistic effects between toluene and C₃H₄ isomers on the formation of polycyclic aromatic hydrocarbons (PAHs) and pyrolysis reactivity. Co-pyrolysis of toluene-allene and toluene-propyne is investigated in a flow reactor employing synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) at 0.04 bar and 1 bar. Mole fraction profiles of fuels and intermediates up to two-ring PAHs are obtained. A kinetic model for co-pyrolysis of toluene-C₃H₄ isomers is established and examined against the present data. Sampled mass-specific photoionization efficiency (PIE) curves are employed to identify the presence of aliphatic aromatic species, favoring specific perception into interactions between phenyl/benzyl radicals and C₃ species. The synergistic effects observed in this work are not sensitive to the molecular structure of allene and propyne but quite sensitive to the experimental pressures. The reason being that the interactions between phenyl/benzyl radicals and small molecules like CH₃, C₂H₂ and C₃H₃ are pressure dependent. Both experimental and simulation results indicate the essential role of the aliphatically substituted aromatic in the growth reactions. Indene and naphthalene are identified as the predominant C₉H₈ and C₁₀H₈ products respectively, in all cases studied. Channels leading to the formation of indene and naphthalene vary with pressure, according to rate-of-production (ROP) analyses. The phenyl + C₃H₄/C₃H₃ channel and benzyl + C₂H₂ channel make comparable contributions to the formation of indene at 0.04 bar, while the latter channel dominates the formation of indene at 1 bar. Both C₇H₅ + C₃H₃ channel and benzyl + C₃H₃ channel can lead to the formation of naphthalene at 0.04 bar, while the latter channel is more competitive at 1 bar.     

Spectroscopic characterization of a Tm3+:SrGdGa3O7 crystal

3 O₇ crystal have been recorded at room temperature and at approximately 8 K. Room-temperature luminescence lifetimes of ¹D₂, ¹G₄, ³H₄, and ³F₄ states have been measured for Tm concentration ranging from [%at.]0.5 to [%at.]9. Based upon these data the crystal field splitting of luminescent states has been derived and radiative transitions rates have been evaluated. Strong self-quenching of luminescence originating in the ¹G₄ and ³H₄ states has been found in this activator–host combination. Peak emission cross section of the potential laser transition at 1800 nm was determined to be 3.9×10^-21 cm² and the gain coefficient versus wavelength was estimated and discussed. Received: 14 April 1998/Revised version: 10 August 1998     

Adsorbate-substrate bonding and the growth of naphthalene thin films on Ag(1 1 1)

The adsorption kinetics, energetics and growth of naphthalene thin films, from submonolayer to about 10 layers, on a Ag(1 1 1) surface at low temperature in a ultrahigh vacuum chamber are examined by using temperature programmed desorption spectroscopy. The first layer adsorption occurs with a desorption energy of 85 ± 5 kJ/mole and results in an interface dipole of 5 ± 1 D, from charge transfer of approximately 0.2 e from naphthalene to Ag. The surface dipole induced inter-adsorbate repulsion causes the lowering of the adsorption energy within the first layer near the saturation coverage so that the second layer deposition begins before the completion of the first layer. The second layer is a metastable phase with desorption energy, 74 ± 3 kJ/mole, smaller than the multilayer desorption energy of 79 ± 5 kJ/mole. Fractional order desorption kinetics were found for both the metastable and the multilayer phases, suggesting desorption from 2-D islanding and 3-D islanding, respectively.     

Molecular adsorption and growth of naphthalene films on Ag(1 0 0)

The adsorption of naphthalene, vacuum deposited on a Ag(1 0 0) surface, was comprehensively investigated by means of low-energy electron diffraction (LEED), temperature-programmed thermal desorption (TPD) spectroscopy, X-ray photoelectron spectroscopy (XPS), and polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the mono- and multilayer regime. A growth of long-range ordered monolayer at 140 K is observed with LEED. The polarization-dependent C 1s NEXAFS shows that the naphthalene molecules in the monolayer lie almost parallel to the Ag(1 0 0) surface. With increasing film thickness, the molecular orientation turns to upright position. Furthermore, NEXAFS measurements show that in the multilayer regime the molecular orientation depends on the substrate temperature during deposition.     

Sub-Doppler high-resolution excitation spectroscopy of the S1 ← S0 transition of dibenzofuran

Rotationally resolved ultrahigh-resolution fluorescence excitation spectra of the S₁ ← S₀ transition of dibenzofuran have been observed using the technique of crossing a collimated molecular beam and the single-mode UV laser beam. 3291 rotational lines of the band and 3047 rotational lines of the band have been assigned. The band has been found to be a b-type transition, in which the transition moment is along the twofold symmetry axis of this molecule, and only the ΔK_a = ± 1 transitions were observed. The excited state is identified to be the S₁¹A₁(ππ^∗) state. In contrast with this, the band has been found to be an a-type transition in which the transition moment is along the long axis in plane. It indicates that the intensity of this vibronic band arises from vibronic coupling with the S₂¹B₂(ππ^∗) state. We determined the accurate rotational constants and the molecule have been shown to be planar both in the ground and excited states.     

Charge transfer excitons: dynamic theory of vibronic spectra

The vibronic spectra of charge transfer excitons (CTE) in a molecular one-component or alternatingly ordered two-component chain are treated in the framework of a dynamic approach (neglecting thermal excitations of the intramolecular vibrations). The model introduces two mechanisms of coupling between CTEs and vibrational quanta: (1) shift of the equilibrium positions of the nuclei in the ionized donor or acceptor; (2) change of the vibrational frequency in the ionized molecule. This model allows to generalize the simple CTE Hamiltonian and the vibronic Hamiltonian of Frenkel excitons. The linear optical susceptibility is calculated in the vibronic region (one CTE and one vibrational quantum). The double splitting of vibronics of CTEs was analyzed: (1) the splitting connected with the location of the intramolecular vibration on the donors or on the acceptors; (2) the splitting connected with the symmetry of the vibronic spectra (in the degenerate case). The general structure of the vibronic spectra of CTEs is established. It contains structureless absorption lines, which correspond to two-particle bands (the phonon is excited on a neutral molecule neighboring the donor or the acceptor) and Lorentz-type lines of one-particle states, which correspond to the bound propagation of the CTE and the phonon.     

Investigations on the geometrical isomers of astaxanthin: Raman spectroscopy of conjugated polyene chain with electronic and mechanical confinement

Recent research interests in geometrical isomers of astaxanthin (AST) are motivated by their metabolic activities in aquatic animals and human. It has been established that cis‐isomers of AST are selectively absorbed in human plasma during the metabolic process; however, exact absorption mechanism is still unclear. Hence, a detailed investigation of the structural and optical properties of geometrical isomers of AST is required. Among the techniques available for the study of AST and other carotenoids, Raman spectroscopy has been much acclaimed. Raman spectra have been shown to be influenced by the electronic and mechanical confinement effects arising from the conjugated polyene chain of carotenoids. In this work, we present Raman studies of geometrical isomers of AST, along with their optical absorption characteristics. Geometrical isomers of AST were prepared by heating all trans‐AST in solution form, and the isomers were separated using high performance liquid chromatography. Optical absorption spectra of cis‐isomers of AST showed hypsochromic shifts in the main absorption band and formation of new bands at lower wavelengths. A detailed Raman spectral analysis performed on the cis‐isomers of AST showed new modes which have not been observed and accounted for so far. In addition, we demonstrate that the electronic and mechanical confinement effects in the polyene chain of AST play an important role in the Raman spectra of geometrical isomers of AST. It is anticipated that this work will demonstrate that Raman spectroscopy is an important diagnostic tool in distinguishing and identifying the geometrical isomers of AST. Copyright © 2014 John Wiley & Sons, Ltd.     

Spectroscopic characterization of Yb:Sc2O3 transparent ceramics

Yb：Sc2O3 transparent ceramics are fabricated by a conventional ceramic process and sintering in H2 atmosphere. The room-temperature spectroscopic properties are investigated, and the Raman spectrum shows an obvious vibration characteristic band centred at 415 cm-1. There are three broad absorption bands around 891, 937, and 971 nm, respectively. The strongest emission peak is centred at 1.04 μm with a broad bandwidth （11 nm） and an emission cross-section of 1.8×10^-20 cm^2. The gain coefficient implies a possible laser ability in a range from 990 nm to 1425 nm. The energy-level structure shows that Yb：Sc2O3 ceramics have large Stark splitting at the ground state level due to their strong crystal field. All the results show that Yb：Sc2O3 transparent ceramics are a promising material for short pulse lasers.     

Spectroscopic characterisation of LaGaO3:Er3+ crystals

LaGaO₃ crystals doped with Er³⁺ ions were grown by the Czochralski method and their optical properties were examined. The Er³⁺ energy levels have been determined from the low-temperature absorption and emission spectra. The results of Judd–Ofelt analysis are presented and compared with experimental data. The emission cross sections are determined for the ⁴ I _13/2→⁴ I _15/2 (1.55 μm) and ⁴ I _11/2→⁴ I _13/2 (2.85 μm) transitions of erbium. Received: 6 December 1999 / Revised version: 10 February 2000 / Published online: 27 April 2000     

Synthesis and structural characterization of Zn_3N_2 powder

1 Introduction In the field of wide band gap semiconductors, many studies have been carried out on zinc compounds. For example, ZnO, as a semiconductor material of n-type with a wide direct band gap of 3.37 eV[1—3], can function as transparent conducting films of low cost; ZnO, with an extremely large exciton binding energy of 60 meV and a strong ultra- violet (UV) stimulated emission at room temperature, has enormous potential for serving as short-wave light devices[4], such as light-emit…     

Steric effect of methyl, methoxy, and ethyl substituents on the excimer formation of naphthalene on Al2O3(0 0 0 1)

Structural relaxation of molecules on surfaces can be monitored by observing the spectral evolution as increasing amount of thermal energy is made available. Naphthalene forms excimers in the excited state when amorphously prepared, but relaxes to a more ordered state when heated. Substituent groups on the naphthalene can substantially alter the available pathways during the thermally induced structural relaxation, and is reflected in the formation of excimer or trap fluorescence. A general correlation was determined for the naphthalene substitution with methyl, methoxy, and ethyl groups on the 1- and 2-positions with the pathway taken by the molecular adlayer.     

Spectroscopic and structural investigations of α‐, β‐, and γ‐AlH3 phases

With its reputation as a high‐energy density fuel, aluminum hydride (AlH₃) has received renewed attention as a material that is particularly suitable, not only for hydrogen storage but also for rocket propulsion. While the various phases of AlH₃ have been investigated theoretically, there is a shortage of experimental studies corroborating the theoretical findings. In response to this, we present here an investigation of these compounds based primarily on two research areas in which there is the greatest scarcity of information in the literature, namely Raman and infrared (IR) absorption analysis. To the authors' knowledge, this is the first report of experimental far‐IR absorption results on these compounds. Two different samples prepared by broadly similar ethereal reactions of AlCl₃ with LiAlH₄ were analyzed. Both Raman and IR absorption measurements indicate that one sample is purely γ‐AlH₃ and that the other is a mixture of α‐, β‐, and γ‐AlH₃ phases. X‐ray diffraction confirms the spectroscopic findings, most notably for the β‐AlH₃ phase, for which optical spectroscopic data are reported here for the first time. Copyright © 2010 John Wiley & Sons, Ltd.     

Spectroscopic characterization of low-nickel copper welding with pulsed Nd:YAG laser

Effects of various operating parameters of 400 W pulsed Nd:YAG laser on welding of nickel-alloyed copper have been investigated. The induced plume spectra in case of using different assist gases and preheat temperatures have been analyzed and the effects of these key factors on melt features such as penetration depth, porosity and spattering have been attributed to the spectroscopic behavior of the plume. Moreover, the CuI electron temperature and its standard deviation as the spectroscopic responses of the plasma plume to various laser process parameters have been quantitatively evaluated at different average and peak powers and pulse energies. Also, the mentioned responses were utilized to justify the weld bead profile features, involving weld depth, width and their stabilities, at similar process parameters. The operating conditions of welding were optimized, regarding the results of spectroscopic observations and attributing them to the qualitative aspects of the melt pool.     

Identification and structural characterization of the synthetic cannabinoid 3-(1-adamantoyl)-1-pentylindole as an additive in 'herbal incense'

Since the end of 2010, more than 20 synthetic cannabimimetics have been identified in 'Spice' products, demonstrating the enormous dynamic in this field. In an effort to cope with the problem, many countries have already undertaken legal measures by putting some of these compounds under control. Nevertheless, once a number of compounds were scheduled, they were soon replaced by other synthetic cannabinoids. In this article, we report the identification of a new--and due to its substitution pattern rather uncommon--cannabimimetic found in several 'herbal incense' products. The GC-EI mass spectrum first led to misidentification as the alpha-methyl-derivative of JWH-250. However, since both substances show different retention indices, thin-layer chromatography was used to isolate the unknown compound. After application of nuclear magnetic resonance spectroscopy, high-resolution MS and GC-MS/MS techniques, the compound was identified as 3-(1-adamantoyl)-1-pentylindole, a derivative of JWH-018 carrying an adamantoyl moiety instead of a naphthoyl group. This finding supports that the listing of synthetic cannabinoids as prohibited substances triggers the appearance of compounds with uncommon substituents. Moreover, it emphasizes the necessity of being aware of the risk of misidentification when using techniques sometimes providing only limited structural information like GC-MS.     

13C NMR of Some Products Obtained by Alkylation of 3,4-Methyl-endioxyphenol with 1-Bromo-3-methylbut-2-ene

¹³C NMR spectra of a series of compounds obtained by alkylating 3,4-methylendioxyphenol with 1-bromo-3-methylbut-2-ene have been taken and the spectral peaks have been assigned.     

Evidence of resonance energy transfer in molecular bilayers on Al2O3 (0 0 0 1)

Energy transfer between aromatic molecules was observed on a dielectric surface. The donor and acceptor molecules were vacuum deposited as bilayers and the surface temperature was linearly ramped in a temperature programmed desorption experiment (TPD). During the TPD procedure, the luminescence of the surface molecules was monitored as a function of temperature. Close to the desorption temperature of the lower layer, mixing of the layers occurred that resulted in energy transfer.