Liquid-Vapor Equilibrium of Multicomponent Cryogenic Systems

Liquid-vapor and solid-vapor equilibria at low to moderate pressures and low temperatures are important in many solar system environments, including the surface and clouds of Titan, the clouds of Uranus and Neptune, and the surfaces of Mars and Triton. The familiar cases of ideal behavior are limiting cases of a general thermodynamic representation for the vapor pressure of each component in a homogeneous multicomponent system. The fundamental connections of laboratory measurements to thermodynamic models are through the Gibbs-Duhem relation and the Gibbs-Helmholtz relation. Using laboratory measurements of the total pressure, temperature, and compositions of the liquid and vapor phases at equilibrium, the values of these parameters can be determined. The resulting model for vapor-liquid equilibrium can then conveniently and accurately be used to calculate pressures, compositions, condensation altitudes, and their dependencies on changing climatic conditions. A specific system being investigated is CH4-C2H6-N2, at conditions relevant to Titan's surface and atmosphere. Discussed are: the modeling of existing data on CH4-N2, with applications to the composition of Titan's condensate clouds; some new measurements on the CH4-C2H6 binary, using a high-precision static/volumetric system, and on the C2H6-N2 binary, using the volumetric system and a sensitive cryogenic flow calorimeter; and describe a new cryogenic phase-equilibrium vessel with which we are beginning a detailed, systematic study of the three constituent binaries and the ternary CH4-C2H6-N2 system at temperatures ranging from 80 to 105 K and pressures from 0.1 to 7 bar

Characterization of 40-Gbit/s pulses generated using a lithium niobate modulator at 1550 nm using frequency resolved optical gating

The characteristics of 40-Gbit/s pulses generated by exploiting the nonlinear characteristics of a Mach-Zender Lithium Niobate modulator are presented. A high spectral resolution frequency resolved optical gating apparatus has been developed to allow for the complete characterization of the intensity and phase of these pulses. The use of these measurements to simplify the design and optimization of an 80-Gbit/s pulse source, based on this 40-Gbit/s source followed by a nonlinear fiber compressor and multiplexer, is also demonstrated

Strength of π-Stacking, from Neutral to Cation: Precision Measurement of Binding Energies in an Isolated π-Stacked Dimer

π-Stacking interactions are ubiquitious across chemistry and biochemistry, impacting areas from organic materials and photovoltaics to biochemistry and DNA. However, experimental data is lacking regarding the strength of π-stacking forces—an issue not settled even for the simplest model system, the isolated benzene dimer. Here, we use two-color appearance potential measurements to determine the binding energies of the isolated, π-stacked dimer of fluorene (C13H10) in ground, excited, and ionic states. Our measurements provide the first precise values for π-stacking interaction energies in these states, which are key benchmarks for theory. Indeed, theoretical predictions using ab initio and carefully benchmarked DFT methods are in excellent agreement with experiment

Discovery of An Unusually Blue L Dwarf Within 10 pc of the Sun

We report the discovery of an unusually blue L5 dwarf within 10 pc of the Sun from a search of Sloan Digital Sky Survey (SDSS) spectra. A spectrophotometric distance estimate of 8.0+/-1.6 pc places SDSS J141624.08+134826.7 among the six closest known L dwarfs. SDSS 1416+13 was overlooked in infrared color-based searches because of its unusually blue J-K_S color, which also identifies it as the nearest member of the blue L dwarf subclass. We present additional infrared and optical spectroscopy from the IRTF/SpeX and Magellan/MagE spectrographs and determine UVW motions that indicate thin disk kinematics. The inclusion of SDSS 1416+13 in the 20 pc sample of L dwarfs increases the number of L5 dwarfs by 20% suggesting that the L dwarf luminosity function may be far from complete.Comment: 15 pages, 3 figures, accepted for publication in AJ; updated version includes corrected radial velocit

The Role of Torsional Dynamics on Hole and Exciton Stabilization in π‐Stacked Assemblies: Design of Rigid Torsionomers of a Cofacial Bifluorene

Exciton and charge delocalization across π‐stacked assemblies is of importance in biological systems and functional polymeric materials. To examine the requirements for exciton and hole stabilization, cofacial bifluorene (F2) torsionomers were designed, synthesized, and characterized: unhindered (model) MeF2, sterically hindered tBuF2, and cyclophane‐like CF2, where fluorenes are locked in a perfect sandwich orientation via two methylene linkers. This set of bichromophores with varied torsional rigidity and orbital overlap shows that exciton stabilization requires a perfect sandwich‐like arrangement, as seen by strong excimeric‐like emission only in CF2 and MeF2. In contrast, hole delocalization is less geometrically restrictive and occurs even in sterically hindered tBuF2, as judged by 160 mV hole stabilization and a near‐IR band in the spectrum of its cation radical. These findings underscore the diverse requirements for charge and energy delocalization across π‐stacked assemblies

Andrew Melville, sacred chronology and world history: the Carmina Danielis 9 and the Antichristus

The accepted view of the ecclesiastical reformer Andrew Melville (1545–1622) as the dynamic leader of the Presbyterian movement in Jacobean Scotland has been severely eroded in recent years, with particular criticism of the actual importance of his contribution to the Kirk and to Scottish higher education. While this reductionism has been necessary, it has resulted in an inversion of the overwhelmingly positive traditional image of Melville, and does not give us a rounded assessment of his life and works. This article attempts to partially redress this balance by looking at a neglected aspect of Melville's Latin writings, which showcase his talents as a humanist intellectual and biblical commentator. It focuses on two long poems that are both commentaries and paraphrases of Daniel and Revelation: the Carmina Danielis and the Antichristus. Through these poems, we see how Melville engaged with two problems exercising reformed theologians across Europe: the dating of key biblical events and the historicised meaning of prophecies within these texts. We also find evidence that Melville read widely among both contemporary and ancient commentators on both these issues

Chromatic dispersion monitoring for high-speed WDM systems using two-photon absorption in a semiconductor microcavity

This paper presents a theoretical and experimental investigation into the use of a two-photon absorption (TPA) photodetector for use in chromatic dispersion (CD) monitoring in high-speed, WDM network. In order to overcome the inefficiency associated with the nonlinear optical-to-electrical TPA process, a microcavity structure is employed. An interesting feature of such a solution is the fact that the microcavity enhances only a narrow wavelength range determined by device design and angle at which the signal enters the device. Thus, a single device can be used to monitor a number of different wavelength channels without the need for additional external filters. When using a nonlinear photodetector, the photocurrent generated for Gaussian pulses is inversely related to the pulsewidth. However, when using a microcavity structure, the cavity bandwidth also needs to be considered, as does the shape of the optical pulses incident on the device. Simulation results are presented for a variety of cavity bandwidths, pulse shapes and durations, and spacing between adjacent wavelength channels. These results are verified experimental using a microcavity with a bandwidth of 260 GHz (2.1 nm) at normal incident angle, with the incident signal comprising of two wavelength channels separated by 1.25 THz (10 nm), each operating at an aggregate data rate of 160 Gb/s. The results demonstrate the applicability of the presented technique to monitor accumulated dispersion fluctuations in a range of 3 ps/nm for 160 Gb/s RZ data channel

π-π stacking vs. C–H/π interaction: Excimer formation and charge resonance stabilization in van der Waals clusters of 9,9′-dimethylfluorene

Studies of exciton and hole stabilization in multichromophoric systems underpin our understanding of electron transfer and transport in materials and biomolecules. The simplest model systems are dimeric, and recently we compared the gas-phase spectroscopy and dynamics of van der Waals dimers of fluorene, 9-methylfluorene (MF), and 9,9′-dimethylfluorene (F1) to assess how sterically controlled facial encumbrance modulates the dynamics of excimer formation and charge resonance stabilization (CRS). Dimers of fluorene and MF show only excimer emission upon electronic excitation, and significant CRS as evidenced in a reduced ionization potential for the dimer relative the monomer. By contrast, the dimer of F1 shows no excimeric emission, rather structured emission from the locally excited state of a tilted (non π-stacked) dimer, evidencing the importance of C–H/π interactions and increased steric constraints that restrict a cofacial approach. In this work, we report our full results on van der Waals clusters of F1, using a combination of theory and experiments that include laser-induced fluorescence, mass-selected two-color resonant two-photon ionization spectroscopy, and two-color appearance potential measurements. We use the latter to derive the binding energies of the F1 dimer in ground, excited, and cation radical states. Our results are compared with van der Waals and covalently linked clusters of fluorene to assess both the relative strength of π-stacking and C–H/π interactions in polyaromatic assemblies and the role of π-stacking in excimer formation and CRS

Letter. On the activation of [CrCl3{R-SN(H)S-R}] catalysts for selective trimerization of ethene: a freeze-quench Cr K-edge XAFS study

Homogeneous chromium catalysts for the selective conversion of ethene to hex-1-ene are formed from Cr(III) reagents, amino-thioether ligands of the type HN(CH2CH2SR)2, and aluminum reagents. In this study the early activation steps are investigated by EPR, UV-visible and Cr K-edge XAFS spectroscopy; rapid stopped-flow mixing and a freeze-quench allows good quality EXAFS analysis of a species formed in ~ 1 second of reaction. This is shown to involve reduction to Cr(II) and deprotonation of a NH group of the auxiliary ligand. This 4-coordinate metal-center may act as precursor for the coordination of ethene and subsequent selective oligomerization