Quantum Mechanical Study of Sulfuric Acid Hydration: Atmospheric Implications

Temelso, Berhane; Morrell, Thomas E.; Shields, Robert M.; Allodi, Marco A.; Wood, Elena K.; Kirschner, Karl N.; Castonguay, Thomas C.; Archer, Kaye A.; Shields, George C.

doi:10.1021/jp2119026

Cited by 111 publications

(194 citation statements)

References 149 publications

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“…Thus, the maximum at H 2 SO 4 (H 2 O) 2 HSO − 4 is in agreement with the ion-pair structure of the neutral (H 2 SO 4 ) 2 (H 2 O) 2 precursor (i.e. (Re et al, 1999;Temelso et al, 2012a, b) suggests that the acidic dissociation occurs. To the best of our knowledge, the H 2 SO 4 dissociation has not yet been studied in the mixed water-sulfuric acid clusters experimentally.…”

Section: Resultssupporting

confidence: 80%

“…We used previously observed energetic minima from literature as the initial structures (Zatula et al, 2011;Husar et al, 2012;Temelso et al, 2012a, b;Henschel et al, 2014) and equilibrated them in molecular dynamics runs to find the most stable isomers. Molecular dynamics were run on the BLYP/6-31+g* potential energy surface, and nuclei were propagated according to classical equations of motion; the constant temperature of 298 K was maintained with a Nosé-Hoover thermostat.…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

“…Progressive hydration of sulfuric acid increases the probability for proton transfer from the acid to water. Theoretical calculations predict the covalently bonded H 2 SO 4 as the global minima for H 2 SO 4 (H 2 O) n clusters with n ≤ 4, while for n = 3 and 4 the hydrogen-bonded (H 2 SO 4 ··· H 2 O) and ion-pair (HSO − 4 ·· · H 3 O + ) structures are energetically very close and both structures coexist for these clusters (Re et al, 1999;Temelso et al, 2012a). Upon further hydration H 2 SO 4 (H 2 O) n for n ≥ 5 the ion-pair structures become the global energy minima.…”

Section: Introductionmentioning

confidence: 99%

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Electron-induced chemistry in microhydrated sulfuric acid clusters

2017

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Abstract. We investigate the mixed sulfuric acid-water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT) calculations. The microhydration of (H 2 SO 4 ) m (H 2 O) n clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H 2 SO 4 ) m (H 2 O) n HSO cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid-water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid-water aerosols are discussed.

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Section: Resultssupporting

confidence: 80%

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electron-induced chemistry in microhydrated sulfuric acid clusters

2017

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“…11,14,15 The main source of H 2 SO 4 in the atmosphere is the emitted SO 2 from fossil fuel and biomass burning, which readily reacts with hydroxyl radicals (cOH) and water vapor. 16,17 Gas-phase H 2 SO 4 has low vapor pressure and can easily supersaturate; 15,18,19 therefore, it has been found that the H 2 SO 4 undergoes a quick gas-condensed phase transition and serves as an effective nucleating species for water vapor, the key nucleating species in the atmosphere.…”

Section: 10-13mentioning

confidence: 99%

Hydration of the methanesulfonate–ammonia/amine complex and its atmospheric implications

et al. 2018

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Methanesulfonate (MSA À ), found in substantial concentrations in the atmosphere, is expected to enhance aerosol nucleation and the growth of nanoparticles, but the details of methanesulfonate clusters are poorly understood. In this study, MSA À was chosen along with ammonia (NH 3 ) or three common amines and water (H 2 O) to discuss the roles of ternary homogeneous nucleation and ion-induced nucleation in aerosol formation. We studied the structural characteristics and thermodynamics of the clusters using density functional theory at the PW91PW91/6-311++G(3df,3pd) level. The analysis of noncovalent interactions predicts that the amines can form more stable clusters with MSA À than NH 3 , in agreement with the results from structures and thermodynamics; however, the enhancement in stability for amines is not large enough to overcome the difference in the concentrations of NH 3 and amines under typical atmospheric conditions. In addition, the favorable free energies of formation for the (MSA

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“…The prime example of this is the complex behaviour of cluster configuration III-i-1 identified by Re et al 6 and here denoted config H. This configuration has been regarded as the most stable ionised configuration for the trihydrated sulphuric acid molecule 6,7,17 , but our results indicate that the structure exhibits both neutral and ionised characteristics at 300 K. This conclusion highlights the limitations of the RRHO approximation 38,39 for free energy estimation using a single optimised structure.…”

Section: Discussionmentioning

confidence: 52%

Empirical valence bonds: A reactive classical potential for sulphuric acid and water

Stinson¹,

Kathmann²,

Ford³

2013

AIP Conference Proceedings

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The nucleation of particles from trace gases in the atmosphere is an important source of cloud condensation nuclei (CCN), and these are vital for the formation of clouds in view of the high supersaturations required for homogeneous water droplet nucleation. The methods of quantum chemistry have increasingly been employed to model nucleation due to their high accuracy and efficiency in calculating configurational energies; and nucleation rates can be obtained from the associated free energies of particle formation. However, even in such advanced approaches, it is typically assumed that the nuclei have a classical nature, which is questionable for some systems. The importance of zero-point motion (also known as quantum nuclear dynamics) in modelling small clusters of sulphuric acid and water is tested here using the path integral molecular dynamics (PIMD) method at the density functional theory (DFT) level of theory. The general effect of zeropoint motion is to distort the mean structure slightly, and to promote the extent of proton transfer with respect to classical behaviour. In a particular configuration of one sulphuric acid molecule with three waters, the range of positions explored by a proton between a sulphuric acid and a water molecule at 300 K (a broad range in contrast to the confinement suggested by geometry optimisation at 0 K) is clearly affected by the inclusion of zero point motion, and similar effects are observed for other configurations.

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Quantum Mechanical Study of Sulfuric Acid Hydration: Atmospheric Implications

Cited by 111 publications

References 149 publications

Electron-induced chemistry in microhydrated sulfuric acid clusters

Electron-induced chemistry in microhydrated sulfuric acid clusters

Hydration of the methanesulfonate–ammonia/amine complex and its atmospheric implications

Empirical valence bonds: A reactive classical potential for sulphuric acid and water

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