Infrared matrix isolation study of H2SO4 and its complexes with H2O

Givan, A.; Larsen, Lars A.; Loewenschuss, A.; Nielsen, Claus J.

doi:10.1039/a706675i

Cited by 58 publications

(100 citation statements)

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“…Concerning the global minimum of the 1:1 complex of sulfuric acid with water, we find that the water molecule is attached in a similar manner to sulfuric acid, as was found both from independent ab initio calculations (79-81) and IR matrix isolation studies (82). We did not find evidence for any ionic character of the 1:1 and also 1:2 sulfuric acid-water minima, which also agrees with the experimental (82) and theoretical findings (84). On the other hand, the global minimum we find for the 1:2 complex differs from the one assumed in the literature to be the global minimum (81).…”

Section: Resultssupporting

confidence: 78%

Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO ₃ to H ₂ SO ₄

Loerting

Liedl

2000

Proc. Natl. Acad. Sci. U.S.A.

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Section: Resultssupporting

confidence: 78%

Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO ₃ to H ₂ SO ₄

Loerting

Liedl

2000

Proc. Natl. Acad. Sci. U.S.A.

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“…The sum of the differences between the nine experimentally observed vibrational wavenumbers 43 and the corresponding computed wavenumbers is 219 cm -1 for our results and 104 cm -1 for those of Miller et al This is probably due to the higher accuracy of the CC-VSCF and MP2 methods. However, for the purposes of thermochemical analysis, also our anharmonic computations are a significant improvement over the harmonic approximation.…”

Section: Resultscontrasting

confidence: 42%

Ab Initio and Density Functional Theory Reinvestigation of Gas-Phase Sulfuric Acid Monohydrate and Ammonium Hydrogen Sulfate

et al. 2006

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We have calculated the thermochemical parameters for the reactions H 2 SO 4 + H 2 O T H 2 SO 4 ‚H 2 O and H 2 -SO 4 + NH 3 T H 2 SO 4 ‚NH 3 using the B3LYP and PW91 functionals, MP2 perturbation theory and four different basis sets. Different methods and basis sets yield very different results with respect to, for example, the reaction free energies. A large part, but not all, of these differences are caused by basis set superposition error (BSSE), which is on the order of 1-3 kcal mol -1 for most method/basis set combinations used in previous studies. Complete basis set extrapolation (CBS) calculations using the cc-pV(X+d)Z and aug-ccpV(X+d)Z basis sets (with X ) D, T, Q) at the B3LYP level indicate that if BSSE errors of less than 0.2 kcal mol -1 are desired in uncorrected calculations, basis sets of at least aug-cc-pV(T+d)Z quality should be used. The use of additional augmented basis functions is also shown to be important, as the BSSE error is significant for the nonaugmented basis sets even at the quadruple-level. The effect of anharmonic corrections to the zero-point energies and thermal contributions to the free energy are shown to be around 0.4 kcal mol -1 for the H 2 SO 4 ‚H 2 O cluster at 298 K. Single-point CCSD(T) calculations for the H 2 SO 4 ‚H 2 O cluster also indicate that B3LYP and MP2 calculations reproduce the CCSD(T) energies well, whereas the PW91 results are significantly overbinding. However, basis-set limit extrapolations at the CCSD(T) level indicate that the B3LYP binding energies are too low by ca. 1-2 kcal/mol. This probably explains the difference of about 2 kcal mol -1 for the free energy of the H 2 SO 4 + H 2 O T H 2 SO 4 ‚H 2 O reaction between the counterpoise-corrected B3LYP calculations with large basis sets and the diffusion-based experimental values of S. M. Ball, D. R. Hanson, F. L Eisele and P. H. McMurry (J. Phys. Chem. A. 2000, 104, 1715. Topological analysis of the electronic charge density based on the quantum theory of atoms in molecules (QTAIM) shows that different method/basis set combinations lead to qualitatively different bonding patterns for the H 2 SO 4 ‚NH 3 cluster. Using QTAIM analysis, we have also defined a proton transfer degree parameter which may be useful in further studies.

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“…Physical properties of both HNO 3 and H 2 SO 4 solutions [2] under stratospheric conditions are previously carried out. Infrared optical constants of this ternary system for different mixtures of H 2 SO 4 and HNO 3 solutions [3][4][5] are evaluated at stratospheric temperature range [6][7][8][9] from 183 K to 293 K. Furthermore, four data sets are tested in the H 2 SO 4 /H 2 O system as well as two data sets in the HNO 3 /H 2 O system [10][11][12][13] revealing partly significant discrepancies in aerosol properties with those parameters recovered from FTIR spectra in the literature data. Rapid temperature fluctuations are shown to cause liquid H 2 SO 4 /HNO 3 /H 2 O stratospheric aerosols [14] to depart considerably from thermodynamic equilibrium.…”

Section: Introductionmentioning

confidence: 95%

Facet shapes and thermo-stabilities of H2SO4•HNO3 hydrates involved in polar stratospheric clouds

Verdes

Paniagua

2015

J Mol Model

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The nucleation, ice crystal shapes and thermodynamic stability of polar stratospheric clouds particles are interesting concerns owing to their implication in the ozone layer destruction. Some of these particles are formed by conformers of H2O, HNO3, and H2SO4. We carried out calculations using density functional theory (DFT) to obtain optimized structures. Several stable trimers are achieved -divided in two groups, one with HNO3 moiety, second with H2SO4 moiety- after pre-optimization at B3LYP/6-31G and subsequently optimization at B3LYP/aug-cc-pVTZ level of theory. For both most stable conformers five H2O molecules are added to their optimized trimers to calculate hydrated geometries. The OH stretching harmonic frequencies are provided for all aggregates. The zero-point energy correction (ZEPC), relative electronic energies (∆E), relative reaction Gibbs free energies ∆(∆G)k-relative, and cooling constant (K cooling ) are reported at three temperatures: 188 K, 195 K, and 210 K. Shapes given in our calculations are compared with various experimental shapes as well as comparisons with their thermo-stabilities.

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Infrared matrix isolation study of H2SO4 and its complexes with H2O

Cited by 58 publications

References 0 publications

Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO ₃ to H ₂ SO ₄

Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO ₃ to H ₂ SO ₄

Ab Initio and Density Functional Theory Reinvestigation of Gas-Phase Sulfuric Acid Monohydrate and Ammonium Hydrogen Sulfate

Facet shapes and thermo-stabilities of H2SO4•HNO3 hydrates involved in polar stratospheric clouds

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Infrared matrix isolation study of H2SO4 and its complexes with H2O

Cited by 58 publications

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Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO 3 to H 2 SO 4

Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO 3 to H 2 SO 4

Ab Initio and Density Functional Theory Reinvestigation of Gas-Phase Sulfuric Acid Monohydrate and Ammonium Hydrogen Sulfate

Facet shapes and thermo-stabilities of H2SO4•HNO3 hydrates involved in polar stratospheric clouds

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Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO ₃ to H ₂ SO ₄

Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO ₃ to H ₂ SO ₄