Raman Spectroscopic Studies of Methane Gas Hydrates

Abstract

A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory.     

Synthesis and Rearrangement of P‐Nitroxyl‐Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study

Low‐temperature generation of P‐nitroxyl phosphane 2 (Ph₂POTEMP), which was obtained by the reaction of Ph₂PH ( 1 ) with two equivalents of TEMPO, is presented. Upon warming, phosphane 2 decomposed to give P‐nitroxyl phosphane P‐oxide 3 (Ph₂P(O)OTEMP) as one of the final products. This facile synthetic protocol also enabled access to P‐sulfide and P‐borane derivatives 7 and 13 , respectively, by using Ph₂P(S)H ( 6 ) or Ph₂P(BH₃)H ( 11 ) and TEMPO. Phosphane sulfide 7 revealed a rearrangement to phosphane oxide 8 (Ph₂P(O)STEMP) in CDCl₃ at ambient temperature, whereas in THF, thermal decomposition of sulfide 7 yielded salt 10 ([TEMP‐H₂][Ph₂P(S)O]). As well as EPR and detailed NMR kinetic studies, indepth theoretical studies provided an insight into the reaction pathways and spin‐density distributions of the reactive intermediates.     

New Experimental Insight into the Nature of Metal−Metal Bonds in Digallium Compounds: J Coupling between Quadrupolar Nuclei

Multiple bonding between atoms is of ongoing fundamental and applied interest. Here, we report a multinuclear (¹H, ¹³C, and ⁷¹Ga) solid‐state magnetic resonance spectroscopic study of digallium compounds which have been proposed, albeit somewhat controversially, to contain single, double, and triple Ga?Ga bonds. Of particular relevance to the nature of these bonds, we have carried out two‐dimensional ⁷¹Ga J/D‐resolved NMR experiments which provide a direct measurement of J(⁷¹Ga,⁷¹Ga) spin–spin coupling constants across the gallium?gallium bonds. When placed in the context of clear‐cut experimental data for analogous singly, doubly, and triply bonded carbon spin pairs or boron spin pairs, the ⁷¹Ga NMR data clearly support the notion of a different bonding paradigm in the gallium systems. Our findings are consistent with an increasing role across the purported gallane–gallene–gallyne series for classical and/or slipped π‐type bonding orbitals.     

Synthesis and nanoimprinting of high refractive index and highly transparent polythioethers based on thiol-ene click chemistry

This work demonstrates the UV nanoimprinting lithography (UV-NIL) of high refractive index and highly transparent polythioethers based on thiol-ene click chemistry. Herein, 9,9-bis(3-mercaptopropylphenylether)fluorene (BMPF) is designed as a new thiol monomer with a high refractive index, high transparency, and good processability for UV-NIL. Colorless polythioethers are synthesized from BMPF and ene monomers under mild thiol-ene click reaction conditions. Excellent transmittance (96%) of 400 nm light is observed in all the polymer films and high refractive index values of 1.5972–1.6382 are attained. UV-NIL using thiol-ene photopolymerization affords polymer nanoimprinting patterns with various features on the order of 100–500 nm without any fractures. To the best of our knowledge, this is the first report on UV-NIL of high refractive index and highly transparent polymers. Through proper monomer and polymer design, novel polythioethers with suitable glass transition temperature (T _g) values are developed with high refractive index, high transparency, and good UV-NIL processability. Furthermore, UV-NIL based on thiol-ene click chemistry is accomplished at the nanoscale. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2175–2182     

Testing the reliability of non-LTE spectroscopic models for complex ions

Collisional-radiative atomic models are widely used to help diagnose experimental plasma conditions through fitting and interpreting measured spectra. Here we present the results of a code comparison in which a variety of models determined plasma temperatures and densities by finding the best fit to an experimental L-shell Kr spectrum from a well characterized, but not benchmarked, laser plasma. While variations in diagnostic strategies and qualities of fit were significant, the results generally confirmed the typically quoted uncertainties for such diagnostics of ±20% in electron temperature and factors of about two in density. The comparison also highlighted some model features important for spectroscopic diagnostics: fine structure was required to match line positions and relative intensities within each charge state and for density diagnostics based on emission from metastable states; an extensive configuration set was required to fit the wings of satellite features and to reliably diagnose the temperature through the inferred charge state distribution; and the inclusion of self-consistent opacity effects was an important factor in the quality of the fit.     

Predicting future duration from present age: A critical assessment

Using a temporal version of the Copernican principle, Gott has proposed a statistical predictor of future longevity based on present age (Gott III, J. R., 1993, Nature, 363, 315) and applied the predictor to a variety of examples, including the longevity of the human species. Although Gott's proposal contains a grain of truth, it does not have the universal predictive power that he attributes to it.     

Electric field‐induced birefringence,optical rotatory power and conoscopic measurements of a chiral antiferroelectric smectic liquid crystal

Using a photoelastic modulator‐based novel set‐up, the electric field‐induced in‐plane birefringence and the optical rotatory power (ORP) were measured of an antiferroelectric liquid crystalline compound (12OF1M7) in its various phases using 30 µm homeotropic cells. Some specific signatures of the in‐plane birefringence and of the ORP for the various phases are being established. A relatively small threshold field is needed for the unwinding process of the antiferroelectric phase with a unit cell of four layers [SmC_A*(1/2)] compared with that for two layers [SmC_A*(0)]. On application of the electric field on the high temperature side of the SmC_A*(1/2) phase (80.1–81.5°C), a field‐induced phase transition is shown to occur directly to the SmC* phase, whereas on the lower temperature side (79.4–80.1°C) the transition takes place to SmC* via the SmC_A*(1/3) phase. The in‐plane birefringence exhibits a critical power law dependence for the SmC*–SmA transition. The ORP changes sign within the temperature range of the phase with a unit cell of three layers, reflecting a change in the handedness during this phase. Using tilted conoscopy, the results for the biaxiality and the apparent tilt angle for a smectic liquid crystal with a tilt angle greater than 18° in the ferroelectric phase are reported. The biaxiality implies the difference in the refractive indices between the two minor axes of the refractive index ellipsoid. The optical transmittance at visible and IR wavelengths for free‐standing films reveal characteristic reflection bands for these phases. The modulated structures of the reflected bands appear just above the SmC_A* phase and below SmC_A*(1/3); these are possibly due to an easy deformation of the phase by the surfaces.     

Control of Protonated Schiff Base Excited State Decay within Visual Protein Mimics: A Unified Model for Retinal Chromophores

Artificial biomimetic chromophore-protein complexes inspired by natural visual pigments can feature color tunability across the full visible spectrum. However, control of excited state dynamics of the retinal chromophore, which is of paramount importance for technological applications, is lacking due to its complex and subtle photophysics/photochemistry. Here, ultrafast transient absorption spectroscopy and quantum mechanics/molecular mechanics simulations are combined for the study of highly tunable rhodopsin mimics, as compared to retinal chromophores in solution. Conical intersections and transient fluorescent intermediates are identified with atomistic resolution, providing unambiguous assignment of their ultrafast excited state absorption features. The results point out that the electrostatic environment of the chromophore, modified by protein point mutations, affects its excited state properties allowing control of its photophysics with same power of chemical modifications of the chromophore. The complex nature of such fine control is a fundamental knowledge for the design of bio-mimetic opto-electronic and photonic devices.