Infrared matrix isolation and quantum chemical studies of the nitrous acid complexes with water
Introduction
The experimental and theoretical investigation of structural and dynamical properties of small molecular clusters has attracted a great deal of interest in last years [1]. They serve as simple model systems to study intermolecular forces, solvation effects or reaction catalysis on a molecular scale. Of special interest are the hydrogen bonded clusters containing water molecules [2], [3], [4]. This is due to the role the water plays as ubiquitous solvent and in atmospheric and extraterrestrial chemistry.
The constitution and structure of clusters in the gas phase has been investigated by the combination of various laser and mass spectroscopies and molecular beam techniques [1]. Matrix isolation technique combined with FTIR spectroscopy has been shown to provide complementary information on bonding and structure of small aggregates. The technique has been used very successfully to study numerous binary molecular complexes. A number of higher order complexes have also been studied by help of matrix isolation spectroscopy. Among them are water [5], [6], methanol [7], ammonia [8], hydrogen halides aggregates [9], [10], ternary complexes containing water and nitrogen [11], water and ethylene [12] and water and hydrogen chloride [13] of stoichiometry 1:2 or 2:1 and ternary complexes containing water, hydrogen chloride and ethylene molecules [12].
We have investigated recently a number of binary complexes of nitrous acid with bases of atmospheric significance [14], [15], [16], [17], [18]. In this paper we present the results of infrared matrix isolation and ab initio studies on the nitrous acid complexes with water and water dimers. The complexes of nitrous acid with water are interesting in atmospheric chemistry due to the presence of nitrous acid and water in the atmosphere, and due to the fact that water is one of the products of decomposition of (HONO)2 dimer.
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Matrix isolation studies
The HONO/H2O/Ar matrices were prepared by simultaneous deposition of HONO/Ar and H2O/Ar mixtures from two separate spray-on lines. Ammonium nitrate was used as a source of nitrous acid and HONO/Ar gas mixtures were prepared in the same way as previously described [14], [15], [16]. The concentration of the HONO/Ar and H2O/Ar mixtures varied in the range 1/300–1/800 and 1/100–1/1000, respectively.
Gas mixtures were prepared by standard manometric techniques and sprayed onto a gold-plated copper
Experimental spectra
The spectra of HONO/Ar [14] and H2O/Ar [5], [23] matrices are in good agreement with those previously reported. In the spectra of matrices with higher HONO concentration bands due to NH4NO2 decomposition products, namely to NH3, NO and NO2, were also present.
Spectra of HONO/H2O/Ar matrices show a number of new absorptions as compared to the spectra of H2O/Ar and HONO/Ar. Most of the product absorptions appeared in the vicinity of trans- and cis-HONO monomer bands. Additional product bands were
Observed spectra
The set of bands observed in the spectra of HONO/H2O/Ar matrices at 3323.0, 1653.5, 1368.1, 873.7 and 672.1 cm−1 close to the trans-HONO absorptions and at 3721.9, 3635.7 cm−1 in the region of water stretching vibrations is assigned to the 1:1 H2O⋯HONO-trans complexes. Irradiation of the matrix with Xe lamp considerably decreased the 3323.0, 1653.5, 1368.1, 873.7, 672.1 and 3721.9, 3635.7 cm−1 bands and increased the 3184.5, 1614.0, 912.9 and 3720.8 cm−1 absorptions. This fact allowed us to
Conclusions
MP2 and DFT calculations indicate that both trans- and cis-HONO isomers form with water molecule three stable 1:1 complexes. In the most stable and complexes the OH group of HONO acts as a proton donor toward an oxygen atom of water molecule. In the other four complexes water molecule serves as a proton donor and an oxygen atom of OH group or an oxygen atom of NO group act as proton acceptors. In complex cyclic hydrogen bond is formed in which two hydrogen
Acknowledgements
The authors would like to gratefully acknowledge Z. Latajka for helpful discussion, comment and critical reading of the manuscript. A.O-M. acknowledges the Wrocław Supercomputer Centre for providing computer time and facilities.
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