0000000001331150
AUTHOR
Markku Räsänen
Internal Rotation in Propionic Acid: Near-Infrared-Induced Isomerization in Solid Argon
The conformational system of propionic acid (CH3CH2COOH) is studied in solid argon. It is predicted by the ab initio calculations that this molecule has four stable conformers. These four structures are denoted Tt, Tg+/-, Ct, and Cg+/-, and they differ by the arrangement around the C-O and Calpha-C bonds. The ground-state Tt conformer is the only form present at 8 K after deposition of an argon matrix containing propionic acid. For the CH3CH2COOH and CH3CH2COOD isotopologues, narrow-band excitation of the first hydroxyl stretching overtone of the conformational ground state promotes the Calpha-C and C-O internal rotations producing the Tg+/- and Ct conformers, respectively. A subsequent vib…
Matrix Isolation and Ab Initio Study of Trans−Trans and Trans−Cis Dimers of Formic Acid
Six trans-trans and five trans-cis dimeric structures of formic acid (HCOOH) are revealed by ab initio calculations. Four trans-trans and two trans-cis dimers are identified in the IR absorption spectra in argon matrices. The trans-cis dimers are obtained by narrow-band IR excitation of the vibrational transitions of the trans-trans dimers. Two trans-trans (tt3 and tt6) and one trans-cis (tc4) dimer are characterized experimentally for the first time. The tunneling decay rates of two trans-cis dimers (tc1 and tc4) are evaluated at different temperatures. A greater lifetime of the trans-cis dimers at elevated temperatures compared to the cis-monomer suggests that the high-energy conformers c…
Formation of HXeO in a xenon matrix: Indirect evidence of production, trapping, and mobility of XeO (1 1Σ+) in solid Xe
IR spectroscopy, laser induced fluorescence (LIF), and thermoluminescence (TL) measurements have been combined to monitor trapping, thermal mobility, and reactions of oxygen atoms in solid xenon. HXeO and O(3) have been used as IR active species that probe the reactions of oxygen atoms. N(2)O and H(2)O have been used as precursors for oxygen atoms by photolysis at 193 nm. Upon annealing of matrices after photolysis, ozone forms at two different temperatures: at 18-24 K from close O ...O(2) pairs and at approximately 27 K due to global mobility of oxygen atoms. HXeO forms at approximately 30 K reliably at higher temperature than ozone. Both LIF and TL show activation of oxygen atoms around 3…
Vibrational spectroscopy of trans and cis deuterated formic acid (HCOOD): Anharmonic calculations and experiments in argon and neon matrices
The absorption spectra of trans and cis conformers of deuterated formic acid (HCOOD) isolated in argon and neon matrices are analyzed in the mid-infrared and near-infrared spectral regions (7900–450 cm � 1 ). Vibrational excitation by narrow-band IR radiation is used to convert the lower-energy trans conformer to the higher-energy cis form. A large number of overtone and combination bands are identified. The results of anharmonic vibrational calculations (CC-VSCF) for both conformers are reported and compared to the experimental spectra.
Dimers of the Higher-Energy Conformer of Formic Acid: Experimental Observation
We report on the first experimental observation of formic acid dimers composed of two molecules of the higher-energy cis conformer. The cis–cis formic acid dimers are prepared in an argon matrix by selective vibrational excitation of the ground state trans conformer (deuterated form HCOOD) combined with thermal annealing of the matrix at about 30 K. Five cis–cis formic acid dimers are predicted by ab initio calculations (interaction energies from −16.9 to −27.2 kJ molˉ¹), and these structures are used for the assignment of the experimental spectra. Selective vibrational excitation of the obtained cis–cis dimers leads to the formation of several trans–cis dimers, which supports the proposed …
Matrix isolation and quantum chemical studies on the H2O2–SO2complex
Complexation and photochemical reactions of hydrogen peroxide and sulfur dioxide have been studied in solid Ar, Kr and Xe. Complexes between H2O2 and SO2 are characterized using Fourier transform infrared spectroscopy and ab initio calculations. In solid Ar, the H2O2–SO2 complex absorptions are found at wavenumbers of 3572.8, 3518.7, 3511.2, 3504.3, 1340.3, 1280.2 and 1149.9 cm−1. In Kr and Xe matrices, the bonded OH stretching frequencies deviate from the values in Ar, and we propose that the matrix surrounding influences the structure of the H2O2–SO2 complex. UV photolysis of the H2O2–SO2 was also studied in solid Ar, Kr and Xe. This photolysis produces mainly a complex between sulfur tri…
Anharmonic Vibrational Spectrum and Experimental Matrix Isolation Study of Thioformic Acid Conformers -- Potential Candidates for Molecular Cloud and Solar System Observations?
Thioformic acid (TFA) is the sulfur analog of formic acid, the simplest organic acid. It has three analogues HCOSH, HCSOH, and HCSSH, each of them having two rotational isomeric (rotameric) forms: trans and cis where the trans form is energetically more stable. In this article, we study computational energetics and anharmonic vibrational spectrum of TFA including overtone and combination vibrations. We also studied experimental photoisomerization and photodecomposition channels of HCOSH molecules with different wavelengths. We suggest that TFA is a potential sulfur containing candidate molecule for interstellar and planetary observations and discuss these in a light of different radiation e…
A study on stabilization of HHeF molecule upon complexation with Xe atoms
In the present work, we computationally study energetic stabilization of HHeF by its complexation with Xe atoms. For the studied HHeF ��� Xen systems ðn ¼ 1–4; 6Þ, we found a large complexation-induced decrease of energy of HHeF with respect to its dissociation into atoms. As a working hypothesis, we assume that this stabilization effect continues for the larger systems (n > 6) as well. This suggests that dissociation of HHeF via the H–He stretching coordinate might be suppressed and its lifetime might be increased by inserting it into large Xe clusters or matrices. 2004 Elsevier B.V. All rights reserved.
Rotational Isomerism in Acetic Acid: The First Experimental Observation of the High-Energy Conformer
The high-energy conformer of acetic acid (cis-AA) is produced in an Ar matrix by vibrational excitation of the OH stretching overtone of the ground conformational state (trans-AA). IR-absorption spectroscopy provides a clear identification of the reaction product. cis-AA converts back to trans-AA in a time scale of minutes at 8 K by tunneling. http://dx.doi.org/10.1021/ja038341a
Matrix-isolation and ab initio study of the complex between formic acid and xenon
Abstract We report on the identification of the complexes of formic acid (FA) and Xe in an argon matrix. The geometries, interaction energies, reaction barriers, and vibrational spectra of the FA⋯Xe complexes are calculated at the MP2 level of theory. The calculations reveal four structures for the trans-FA⋯Xe complex and four structures for the cis-FA⋯Xe complex. In the experiments, two structures of the trans-FA⋯Xe complex are observed after deposition of FA/Xe/Ar matrices, with and without OH⋯Xe interaction (H-bonded and non-H-bonded structures). The cis-FA⋯Xe complex was synthesized by vibrational excitation of the non-H-bonded trans-FA⋯Xe complex. The non-H-bonded and H-bonded structur…
HXeOBr in a xenon matrix
We report on a new noble-gas molecule HXeOBr prepared in a low-temperature xenon matrix from the HBr and N2O precursors by UV photolysis and thermal annealing. This molecule is assigned with the help of deuteration experiments and ab initio calculations including anharmonic methods. The H−Xe stretching frequency of HXeOBr is observed at 1634 cm−1 , which is larger by 56 cm−1 than the frequency of HXeOH identified previously. The experiments show a higher thermal stability of HXeOBr molecules in a xenon matrix compared to HXeOH. peerReviewed