Quantum mechanical studies of weakly bound molecular clusters

Moore Plummer, Patricia L.

doi:10.1016/0166-1280(94)80123-1

Cited by 14 publications

(24 citation statements)

References 32 publications

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“…The geometry has the planes of the two monomer units tilted by about 45° from a parallel orientation with the oxygen atom of H 2 O closest to the S atom of SO 2 at an S ··· O distance of 282.4(2) pm. This structure is basically in agreement with quantum chemical calculations at various levels of theory (see Figure 1),22,24,25,26 but as we will show below the experimental tilt angle between the two monomers needs to be discussed. The structures of other SO 2 hydrates have been studied theoretically only;22,25,27 this work will also be discussed below.…”

Section: Introductionsupporting

confidence: 88%

“…A smaller tilt angle yields a larger vector sum of the dipole moments. Thus, we believe that our theoretically predicted tilt angle is more reliable, especially since other theoretical methods also resulted in a nearly parallel arrangement of the two monomers 24,25,26. As a consequence of this relatively loose sandwich structure, the G3X(MP2) binding enthalpy at 298 K is only 11.6 kJ mol –1 .…”

Section: Resultsmentioning

confidence: 74%

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Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Steudel

2009

Eur J Inorg Chem

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The structures of a large number of hydrates of sulfur dioxide (SO2·nH2O), of the sulfonate ion ([HSO3]–·nH2O), of the tautomeric hydrogensulfite anion ([SO3H]–·nH2O), and of sulfurous acid (H2SO3·nH2O) with up to eight water molecules attached to these species have been optimized at the B3LYP/6‐31G(2df,p) level of theory (DFT). The calculated vibrational frequencies allow the definite assignment of certain characteristic modes, and in this way a convincing interpretation of published spectra of aqueous SO2 as well as of SO2 adsorbed on very cold ice crystals has been achieved for the first time. Single‐point calculations at the G3X(MP2) level of theory were used to calculate the binding energies of the water molecules in SO2·nH2O as well as the relative stabilities of the isomeric anionic species [HSO3]–·nH2O and [SO3H]–·nH2O. Generally, the water molecules tend to stick together forming clusters, whereas the particular sulfur‐containing molecule remains at the surface of the water cluster, but it is always strongly hydrogen‐bonded. Only when there are more than six water molecules are the anions more or less completely surrounded by water molecules. DFT calculations erroneously predict that the gaseous hydrated sulfonate ions are more stable than the isomeric hydrogensulfite ions, even when hydrated with six water molecules. However, if these hydrated species are calculated as being embedded in a polar continuum simulating the aqueous phase, the hydrogensulfite ions are more stable than the sulfonate ions, in agreement with various spectroscopic observations on aqueous sulfite solutions. On the other hand, at the higher G3X(MP2) level, the gaseous hydrated hydrogensulfite anions are more stable than the corresponding sulfonate ions only if the number of water molecules is larger than four, whereas for the weakly hydrated anions the order of relative energies is reversed. The possible implications of these results for the enzymatic oxidation of “sulfite ions” ([HSO3]– and [SO3H]–) by sulfite oxidase are discussed. The conversion of SO2·6H2O into its isomer H2SO3·5H2O is predicted to be exothermic (ΔH°298 = –56.1 kJ mol–1) and exergonic (ΔG°298 = –22.5 kJ mol–1). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Introductionsupporting

confidence: 88%

Section: Resultsmentioning

confidence: 74%

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Steudel

2009

Eur J Inorg Chem

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“…This optimized structure is in good agreement with those obtained by previous microwave spectroscopy 5 and calculations. 1,17,18 The binding energy of the H 2 O-SO 2 complex is calculated to be 3.3 kcal/ mol which is smaller than that of the H 2 O dimer ͑4.5 kcal/ mol͒.…”

Section: Structures Of the Complexesmentioning

confidence: 87%

“…To our knowledge, the investigations concerning the structure of the ͑H 2 O͒ 2 -SO 2 complex are limited to one experimental study 3 and two quantum chemical calculations. 17,18 Schriver et al 3 concluded that, based on the observed OH stretching frequencies, there are two kinds of bonded OH groups and suggested the cyclic structure. One of the bonded OH stretching bands of the 2:1 complexes is largely redshifted by ϳ90 cm −1 with respect to the corresponding band of the H 2 O dimer, which we have confirmed in the present study.…”

Section: Structures Of the Complexesmentioning

confidence: 99%

Infrared spectra of the (H2O)n–SO2 complexes in argon matrices

Hirabayashi

Ito

Yamada

2006

The Journal of Chemical Physics

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The infrared spectra of the (H(2)O)n-SO(2) complexes trapped in argon matrices have been investigated using Fourier transform infrared spectroscopy. In addition to the 1:1 and 2:1 complexes, the first spectroscopic evidence for the 3:1 complex has been obtained from the spectra of the SO stretching and the OH stretching modes. The observed frequency shifts in the bonded OH stretching region indicate that the hydrogen bonds of the 2:1 and 3:1 complexes are strengthened compared to that of the 1:1 complex, which suggests the cyclic structure of the complexes.

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“…We used as a template the publication of Hargittai [ 87 ], which examined a set of seven likely structural models for the metal dihalides, which we considered candidates as potential structures for the sulphur dioxide dimer. This trial set included three cyclic, two “linear”, and two bifurcated models, most of which were also investigated by other workers [ 3 , 4 , 5 , 6 , 8 , 9 ]. Along with the seven Hargittai structures, we also included two species that involved a S…S interaction, with no expectation that they would be strong candidates for the preferred SO 2 dimer structure, but simply for completeness.…”

Section: Resultsmentioning

confidence: 99%

The Structures, Molecular Orbital Properties and Vibrational Spectra of the Homo- and Heterodimers of Sulphur Dioxide and Ozone. An Ab Initio Study

Ford

2021

Molecules

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The structures of a number of dimers of sulphur dioxide and ozone were optimized by means of a series of ab initio calculations. The dimer species were classified as either genuine energy minima or transition states of first or higher order, and the most probable structures consistent with the experimental data were confirmed. The molecular orbitals engaged in the interactions resulting in adduct formation were identified and relations between the orbitals of the dimers of the valence isoelectronic monomer species were examined. The vibrational spectra of the most probable structures were computed and compared with those reported in the literature, particularly with spectra observed in cryogenic matrices. The calculations were extended to predict the properties of a number of possible heterodimers formed between sulphur dioxide and ozone.

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Quantum mechanical studies of weakly bound molecular clusters

Cited by 14 publications

References 32 publications

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Infrared spectra of the (H2O)n–SO2 complexes in argon matrices

The Structures, Molecular Orbital Properties and Vibrational Spectra of the Homo- and Heterodimers of Sulphur Dioxide and Ozone. An Ab Initio Study

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Quantum mechanical studies of weakly bound molecular clusters

Cited by 14 publications

References 32 publications

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO2·nH2O, [HSO3]–·nH2O, [SO3H]–·nH2O, and H2SO3·nH2O (n = 0–8)

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO2·nH2O, [HSO3]–·nH2O, [SO3H]–·nH2O, and H2SO3·nH2O (n = 0–8)

Infrared spectra of the (H2O)n–SO2 complexes in argon matrices

The Structures, Molecular Orbital Properties and Vibrational Spectra of the Homo- and Heterodimers of Sulphur Dioxide and Ozone. An Ab Initio Study

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Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)