Markku Räsänen

A stable argon compound

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.

Neutral rare-gas containing charge-transfer molecules in solid matrices. III. HXeCN, HXeNC, and HKrCN in Kr and Xe

Ultraviolet‐irradiation of hydrogen halide containing rare gas matrices yields the formation of linear centrosymmetric cations of type (XHX)+, (X=Ar, Kr, Xe). Annealing of the irradiated doped solids produces, along with thermoluminescence, extremely strong absorptions in the 1700–1000 cm−1 region. Based on isotopic substitution and halogen dependence of these bands, the presence of hydrogen and halogen atom(s) in these species is evident. In the present paper we show the participation of rare gas atom(s) in these new compounds. The evidence is based on studies of the thermally generated species in mixed rare gas matrices. The new species are assigned as neutral charge‐transfer molecules HX+Y− (Y=halogen), and their vibrational spectra are discussed and compared with those calculated with ab initio methods. This is the first time hydrogen and a rare gas atom has been found to make a chemical bond in a neutral stable compound. The highest level ab initio calculations on the existence of compounds of type H...

Noble-Gas Hydrides: New Chemistry at Low Temperatures

Noble-gas chemistry has been undergoing a renaissance in recent years, due in large part to noble-gas hydrides, HNgY, where Ng = noble-gas atom and Y = electronegative fragment. These molecules are exceptional because of their relatively weak bonding and large dipole moments, which lead to strongly enhanced effects of the environment, complexation, and reactions. In this Account, we discuss the matrix-isolation synthesis of noble-gas hydrides, their spectroscopic and structural properties, and their stabilities.This family of species was discovered in 1995 and now has 23 members that are prepared in noble-gas matrices (HXeBr, HKrCl, HXeH, HXeOH, HXeO, etc.). The preparations of the first neutral argon molecule, HArF, and halogen-free organic noble-gas molecules (HXeCCH, HXeCC, HKrCCH, etc.) are important highlights of the field. These molecules are formed by the neutral H + Ng + Y channel. The first addition reaction involving HNgY molecules was HXeCC + Xe + H --> HXeCCXeH, and this led to the first hydride with two noble-gas atoms (recently extended by HXeOXeH). The experimental synthesis of HNgY molecules starts with production of H and Y fragments in solid noble gas via the UV photolysis of suitable precursors. The HNgY molecules mainly form upon thermal mobilization of the fragments.One of the unusual properties of these molecules is the hindered rotation of some HNgY molecules in solid matrices; this has been theoretically modeled. HNgY molecules also have unusual solvation effects, and the H-Xe stretching mode shifts to higher frequencies (up to about 150 cm-1) upon interaction with other species.The noble hydrides have a new bonding motif: HNgY molecules can be represented in the form (H-Ng)+Y-, where (H-Ng)+ is mainly covalent, whereas the interaction between (HNg)+ and Y- is predominantly ionic. The HNgY molecules are highly metastable species representing high-energy materials. The decomposition process HNgY --> Ng + HY is always strongly exoergic; however, the decomposition is prevented by high barriers, for instance, about 2 eV for HXeCCH. The other decomposition channel HNgY --> H + Ng + Y is endothermic for all prepared molecules.Areas that appear promising for further study include the extension of argon chemistry, preparation of new bonds with noble-gas atoms (such as Xe-Si bond), and studies of radon compounds. The calculations suggest the existence of related polymers, aggregates, and even HNgY crystals, and their experimental preparation is a major challenge. Another interesting task, still in its early stages, is the preparation of HNgY molecules in the gas phase.

Neutral rare-gas containing charge-transfer molecules in solid matrices. II. HXeH, HXeD, and DXeD in Xe

Photolysis of hydrogen halides (and some other hydrogen containing small molecules) in solid Xe yields in a two step process charged centers, one of them being XeHXe+. Annealing of the irradiated doped solids produces, in addition to H–Xe–Y (Y=Cl, Br, or I) species characterized by us previously, a fairly strong doublet at 1181 and 1166 cm−1 and a weak absorption at 701 cm−1. Deuterated precursors yield a doublet at 846 and 856 cm−1. Also peaks belonging to mixed H/D form are found, indicating that the absorbing species contains two H/D atoms. The new species responsible for these absorptions are assigned as neutral linear centrosymmetric HXeH, HXeD, and DXeD. The nature of the bonding can be understood in terms of the resonance between the two ionic forms HXe+H− and H−Xe+H, analogously to the valence bond description of the well known XeF2. The pseudopotential (LANL1DZ) ab initio calculations at the MP2 level are in good agreement with the observed spectra.

Optical gain in Si/SiO2 lattice: Experimental evidence with nanosecond pulses

Experimental evidence of population inversion and amplified spontaneous emission was found for Si nanocrystallites embedded in SiO2 surrounding under pumping with 5 ns light pulses at 380, 400, and 500 nm. As an important property, our experiments show a short lifetime of the population inversion allowing a generation of short (a few nanosecond) amplified light pulses in the Si/SiO2 lattice. The estimate for optical gain in the present samples is 6 cm−1 at 720 nm.

New Rare‐Gas‐Containing Neutral Molecules

The synthesis of novel neutral rare-gas-containing molecules of type HXY, where × = Xe or Kr and Y is an electronegative atom or fragment, is discussed. The molecules are characterised experimentally by their vibrational spectra and computationally by extensive ab initio calculations. They are formed in low-temperature rare-gas solids from neutral reagents and their bonding consists of both covalent and ionic contributions. Our recent studies add to the previously known class of rare-gas chemical bonds in neutral ground-state molecules the new bonds Xe–H, Xe–I, Xe–Br, Xe–S, Kr–H, Kr–C, and Kr–Cl.

Cis→trans conversion of formic acid by dissipative tunneling in solid rare gases: Influence of environment on the tunneling rate

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.

The mechanism of formation and infrared-induced decomposition of HXeI in solid Xe

Ultraviolet (UV) irradiation of HI-doped xenon matrix dissociates the precursor and leads to the formation and trapping of neutral atoms. After UV photolysis, annealing of the matrix mobilizes the hydrogen atoms at about 38 K. The mobilized hydrogen atoms react with I/Xe centers forming HXeI molecules in a diffusion controlled reaction. The formed molecules can be photolyzed with infrared (IR) irradiation at 2950–3800 cm−1 and quantitatively regenerated thermally. The formation of HXeI from neutral atoms is proved by the quantitative correlation between neutral iodine atoms and HXeI molecules in selective IR photodissociation and thermal regeneration experiments. Kinetic measurements show that the formation of HXeI from atoms is prevented by a potential barrier, which is estimated to be 700 cm−1 in magnitude. The potential barrier is proposed to originate from the avoided crossing between neutral H+Xe+I and ionic (HXe)++I− singlet surfaces. The dissociation energy D0 of HXeI with respect to the top of the...

HKrF in solid krypton

A new krypton-containing compound, HKrF, has been prepared in a low-temperature Kr matrix via VUV photolysis of the HF precursor and posterior thermal mobilization of H and F atoms. All three fundamental vibrations have been observed in the FTIR spectra at ∼1950 cm−1 (H–Kr stretch), ∼650 cm−1 (bending), and ∼415 cm−1 (Kr–F stretch). Two distinct sites of HKrF have been identified. The energy difference between the H–Kr stretching vibrations for the two sites is remarkably large (26 cm−1), indicating a strong influence of the environment. In annealing after the photolysis of the precursor, HKrF is formed in two different stages: at 13–16 K from closely trapped H+F pairs and at T>24 K due to more extensive mobility of H and F atoms in the matrix. HKrF in a less stable site decreases at temperatures above 32 K, the other site being stable up to the sublimation temperature of the matrix. The photodecomposition cross section for HKrF has been measured between 193 and 350 nm and compared with the cross sections...

Formation and characterization of neutral krypton and xenon hydrides in low-temperature matrices

A family of rare-gas-containing hydrides HXY (where X=Kr or Xe, and Y is an electronegative fragment) is described. These molecules are experimentally prepared in low-temperature matrices by photodissociation of a hydrogen-containing HY precursor and thermal mobilization of the photodetached hydrogen atoms. The neutral HXY molecules are formed in a concerted reaction H+Y→HXY. Experimental evidence for the formation of these species is essentially based on strong infrared absorption bands that appear after annealing of the photolyzed matrices and are assigned to the H-X stretch of the HXY molecules. Computationally, the formation of these HXY molecules decreases the H-X distance by a factor of ⩾2 from its van der Waals value, which emphasizes their true chemical bonding, possessing both covalent and ionic contributions. The estimated dissociation energies vary from 0.4 to 1.4 eV and hold promise for forthcoming observation of these molecules in the gas phase. The experiments with the HXY molecules widen ou...