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L Khriachtchev

Publications and source records attributed to L Khriachtchev.

5 recordsLinked to original sources
PubMed2004

Rotational isomerism of acetic acid isolated in rare-gas matrices: Effect of medium and isotopic substitution on IR-induced isomerization quantum yield and cis-->trans tunneling rate.

Rotational isomerization of acetic acid (CH3COOH) is studied in Ar, Kr, and Xe matrices. The light-induced trans-->cis reaction is promoted using resonant excitation of a number of modes in the 3500-7000 cm(-1) region, and the quantum yields for this process are measured for various acetic acid isotopologues and matrix materials. For excitation of acetic acid at energies above the predicted isomerization energy barrier (> or =4400 cm(-1)), the measured quantum yields are in average 2%-3%, and this is one order of magnitude smaller than the corresponding values known for formic acid (HCOOH). This difference is interpreted in terms of the presence of the methyl group in acetic acid, which enhances energy relaxation channels competing with the rotational isomerization. This picture is supported by the observed large effect of deuteration of the methyl group on the photoisomerization quantum yield. The trans-->cis reaction quantum yields are found to be similar for Ar, Kr, and Xe matrices, suggesting similar energy relaxation processes for this molecule in the various matrices. The IR-induced cis-->trans process, studied for acetic acid deuterated in the hydroxyl group, shows reliably larger quantum yields as compared with the trans-->cis process. For pumping of acetic acid at energies below the predicted isomerization barrier, the trans-->cis reaction quantum yields decrease strongly when the photon energy decreases, and tunneling is the most probable mechanism for this process. For the cis-->trans dark reaction, the observed temperature and medium effects indicate the participation of the lattice phonons in the tunneling-induced process.

Journal Article↗
PubMed2001

Matrix isolation and ab initio study of the hydrogen-bonded H2O2-CO complex.

The structure, energetics, and infrared spectrum of the H2O2-CO complex have been studied computationally with the use of ab initio calculations and experimentally by FTIR matrix isolation techniques. Computations predict two stable conformations for the H2O2-CO complex, both of which show almost linear hydrogen bonds between the subunits. The carbon-attached HOOH-CO complex is the lower-energy form, and it has an interaction energy of -9.0 kJmol(-1) at the CCSD(T)/6-311++G(3df,3pd)// MP2/6-311++G(3df,3pd) level. The higher-energy form, HOOH-OC, has an interaction energy of 4.7 kJmol(-1) at the same level of theory. Experimentally, only the lower-energy form, HOOH-CO, was observed in Ar, Kr, and Xe matrices, and the hydrogen bonding results in substantial perturbations of the observed vibrational modes of both complex subunits. UV photolysis of the complex species primarily produces a complex between water and carbon dioxide, but minor amounts of HCO and trans-HOCO were found as well.

Journal Article↗
PubMed2000

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.

Journal Article↗
PubMed2000

Vibrational Spectra of cis and trans Oxalyl Fluoride and Their Site-Selective IR-Induced Rotamerization in an Argon Matrix.

A cis/trans equilibrium mixture of matrix-isolated oxalyl fluoride was irradiated with a narrowband tunable IR source in the 2nu (CO) spectral region (3680-3710 cm(-1)). Rotamerization of cis into trans and vice versa was achieved (even site selective) by selective IR pumping. The experiments strongly aided a detailed IR analysis of both rotamers. For a complete vibrational analysis, low-temperature Raman measurements were also performed. With the exception of the torsional vibration of cis oxalyl fluoride, all the fundamentals of both rotamers have been observed. Copyright 2000 Academic Press.

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