The noble gases have a particularly stable electronic configuration, comprising fully filled s and p valence orbitals. This makes these elements relatively non-reactive, and they exist at room temperature as monatomic gases. Pauling predicted in 1933 that the heavier noble gases, whose valence electrons are screened by core electrons and thus less strongly bound, could form stable molecules. This prediction was verified in 1962 by the preparation of xenon hexafluoroplatinate, XePtF6, the first compound to contain a noble-gas atom. Since then, a range of different compounds containing radon, xenon and krypton have been theoretically anticipated and prepared. Although the lighter noble gases neon, helium and argon are also expected to be reactive under suitable conditions, they remain the last three long-lived elements of the periodic table for which no stable compound is known. Here we report that the photolysis of hydrogen fluoride in a solid argon matrix leads to the formation of argon fluorohydride (HArF), which we have identified by probing the shift in the position of vibrational bands on isotopic substitution using infrared spectroscopy. Extensive ab initio calculations indicate that HArF is intrinsically stable, owing to significant ionic and covalent contributions to its bonding, thus confirming computational predictions that argon should form a stable hydride species with properties similar to those of the analogous xenon and krypton compounds reported before.
Structure determination of gold nanoparticles (AuNPs) is necessary for understanding their physical and chemical properties, and only one AuNP larger than 1 nm in diameter, an Au102NP, has been solved to atomic resolution. Whereas the Au102NP structure was determined by X-ray crystallography, other large AuNPs have proved refractory to this approach. Here we report the structure determination of an Au68NP at atomic resolution by aberration-corrected transmission electron microscopy (AC-TEM), performed with the use of a minimal electron dose, an approach that should prove applicable to metal NPs in general. The structure of the Au68NP was supported by small angle X-ray scattering (SAXS) and by comparison of observed infrared (IR) absorption spectra with calculations by density functional theory (DFT).
We report on strong coupling between surface-plasmon polaritons (SPP) and Rhodamine 6G (R6G) molecules, with double vacuum Rabi splitting energies up to 230 and 110 meV. In addition, we demonstrate the emission of all three energy branches of the strongly coupled SPP-exciton hybrid system, revealing features of system dynamics that are not visible in conventional reflectometry. Finally, in analogy to tunable-Q microcavities, we show that the Rabi splitting can be controlled by adjusting the interaction time between waveguided SPPs and R6G deposited on top of the waveguide. The interaction time can be controlled with sub-fs precision by adjusting the length of the R6G area with standard lithography methods.
The relaxation of the higher-energy cis conformer of formic acid to the lower-energy trans form by a tunneling mechanism has been investigated in low-temperature rare gas matrices. In the temperature range 8 -60 K, the tunneling takes place dominantly from the vibrational ground state of the cis form and the temperature dependence of the tunneling rate constant is influenced by the interactions with the environment. The temperature-dependent tunneling rates for HCOOH and DCOOH in solid Ar, Kr, and Xe are measured including data for molecules in different local environments within each host. It was found that the medium and the local environment has a significant influence on the tunneling rate. In reaction kinetics, tunneling of atoms is often negligible compared with over-barrier transitions. At very low temperatures, however, the population of energy states above the barrier becomes exceedingly small and tunneling becomes comparatively more important.1 In a condensed environment, phonons participate in a tunneling reaction and the environment should have some effect on tunneling reactions.2,3 However, in several previous experiments it was found that the tunneling rate constant was unaffected by the change of solvent. 1,4 -6 In this work, we have studied the conversion of cis formic acid ͑HCOOH͒ to trans formic acid in solid rare gases ͑Ar, Kr, Xe͒. This reaction is dominated by tunneling from the vibrational ground state at temperatures below 60 K. The results show that the tunneling rate depends strongly on the environment.The samples were made by mixing vapors of formic acid ͑FA͒ ͑KEBO lab, Ͼ99%͒ or its isotopomers ͑IT Isotope 95%-98% deuteration͒ with rare gases ͑Rg͒ Ar ͑AGA, 99.9999%͒, Kr ͑Air Liquid, 99.95%͒, Xe ͑AGA, 99.997%͒ in the gas phase in a proportion FA/RgϷ1/1000. The gas mixture was deposited on a CsI substrate at 15 K ͑Ar͒, 25 K ͑Kr͒ or 35 K ͑Xe͒ yielding highly monomeric matrices with respect to FA. Thickness of the sample was typically about 100 m. After deposition, the samples were cooled to ϳ8 K which was the lower limit for the cryostat ͑APD DE 202 A͒. The spectra were measured with a FTIR spectrometer ͑Nico-let 60 SX͒ with a resolution of 1 or 0.25 cm Ϫ1 . FA has energy minima in two planar forms differing by orientation of the hydroxyl group as shown in Fig. 1. The interconversion of the conformers involves mainly the torsional motion of the hydroxyl group. In the gas phase, cis-FA is 1365Ϯ30 cm Ϫ1 higher in energy than trans-FA. 7 The barrier from trans to cis has been calculated to be ϳ4200 cm Ϫ1. 8 In this work, cis-FA was prepared by exciting the vibrational transitions of trans-FA in rare-gas matrices with narrowband infrared radiation of an optical parametric oscillator ͑Sunlite, Continuum, FWHM ϳ0.1 cm Ϫ1 ͒. The excitation energy flows into the torsional coordinate inducing the conformer conversion. 9 The IR spectra of cis and trans FA differ significantly from each other making it possible to distinguish them easily in rare-gas matrices.9 FA is trapped in several sites correspo...
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