Sulfuric acid and aromatic carboxylate clusters H2SO4·ArCOO−: Structures, properties, and their relevance to the initial aerosol nucleation

Hou, Gao‐Lei; Valiev, Marat; Wang, Xuebin

doi:10.1016/j.ijms.2019.02.001

Cited by 9 publications

(18 citation statements)

References 72 publications

(97 reference statements)

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“…While isomers 1 , 3 , and 4 may be regarded as HSO4 – ·H 2 CO 3 , isomer 2 is better recognized as H 2 SO4·HCO 3 − , which is only about 2 kJ/mol higher in energy than isomer 1 . Isomer 2 is unexpected solely from gas-phase proton affinity prediction and its stability can be attributed to the formation of two strong hydrogen bonds and highly delocalized extra electrons according to previous findings by Hou et al [ 24 , 27 , 36 , 37 , 38 ]. Such electron delocalization can be partly reflected by the highest occupied molecular orbitals (HOMOs) as presented in Figure S2 .…”

Section: Resultssupporting

confidence: 65%

“…The electron delocalization could partly be reflected by the HOMOs as shown in Figure S2 and partly by the charge distributions as summarized in Table S1 . QTAIM is a useful approach to evaluate the nature of hydrogen bond and its strength in addition to the geometrical analysis [ 37 , 46 ]. According to Bader’s theory, the critical points (3,−3) are the nuclear positions where the charge density is local maximum in all directions, and the BCPs (3,−1) correspond to the second-order saddle points, for which two eigenvalues of the charge density Hessian matrix are negative and one is positive.…”

Section: Resultsmentioning

confidence: 99%

“…Hydrogen bonding is an effective way to stabilize otherwise unstable and uncommon structures [24][25][26][27][28][29][30][31][32][33][34]. For example, Hou et al have performed a series of studies on bisulfate ion-containing complexes, showing that hydrogen bonding interactions can alter the protonation pattern in the complex, which violates the gas-phase proton affinity prediction [24,27,[35][36][37][38]. This motivated us to wonder whether an appropriate partner such as bisulfate ion could also stabilize the exotic conformers of H 2 CO 3 molecule.…”

Section: Molecule In 2011mentioning

confidence: 99%

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Stabilizing the Exotic Carbonic Acid by Bisulfate Ion

Lu¹,

Liu

et al. 2021

Molecules

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Carbonic acid is an important species in a variety of fields and has long been regarded to be non-existing in isolated state, as it is thermodynamically favorable to decompose into water and carbon dioxide. In this work, we systematically studied a novel ionic complex [H2CO3·HSO4]− using density functional theory calculations, molecular dynamics simulations, and topological analysis to investigate if the exotic H2CO3 molecule could be stabilized by bisulfate ion, which is a ubiquitous ion in various environments. We found that bisulfate ion could efficiently stabilize all the three conformers of H2CO3 and reduce the energy differences of isomers with H2CO3 in three different conformations compared to the isolated H2CO3 molecule. Calculated isomerization pathways and ab initio molecular dynamics simulations suggest that all the optimized isomers of the complex have good thermal stability and could exist at finite temperatures. We also explored the hydrogen bonding properties in this interesting complex and simulated their harmonic infrared spectra to aid future infrared spectroscopic experiments. This work could be potentially important to understand the fate of carbonic acid in certain complex environments, such as in environments where both sulfuric acid (or rather bisulfate ion) and carbonic acid (or rather carbonic dioxide and water) exist.

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Section: Resultssupporting

confidence: 65%

Section: Resultsmentioning

confidence: 99%

Section: Molecule In 2011mentioning

confidence: 99%

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Stabilizing the Exotic Carbonic Acid by Bisulfate Ion

Lu¹,

Liu

et al. 2021

Molecules

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“…Figure 6 presents the NIPE spectra of [H 2 SO 4 •ArCOOH− H + ] − clusters (Ar = C 6 H 5 , o,m,p-methyl-C 6 H 5 ) and their optimized low-lying structures. 29 All the spectra show similar EBEs and band profiles, but all with significantly increased EBEs compared to either bisulfate ion (∼4.8 eV) 1 or aromatic carboxylate ions (∼3.6 eV), 48 which illustrates appreciable stabilization due to clustering. Careful examination indicates that all spectra have a weak threshold feature starting from ∼5.50 eV and followed by a main band with a fast-rising edge starting from ∼6.00 eV.…”

Section: Sulfuric Acid−aromatic Organic Ion Clustersmentioning

confidence: 89%

Molecular Specificity and Proton Transfer Mechanisms in Aerosol Prenucleation Clusters Relevant to New Particle Formation

Hou

Wang

2020

Acc. Chem. Res.

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Conspectus Atmospheric aerosol particles influence the Earth’s radiative energy balance and cloud properties, thus impacting the air quality, human health, and Earth’s climate change. Because of the important scientific and overarching practical implications of aerosols, the past two decades have seen extensive research efforts, with emphasis on the chemical compositions and underlying mechanisms of aerosol formation. It has been recognized that new particle formation (NPF) contributes up to 50% of atmospheric aerosols. Nowadays, the general consensus is that NPF proceeds via two distinct stages: the nucleation from gaseous precursors to form critical nuclei of sub-1–2 nm size, and the subsequent growth into large particles. However, a fundamental understanding of both the NPF process and molecular-level characterization of the critical size aerosol clusters is still largely missing, hampering the efforts in developing reliable and predictive aerosol nucleation and climate models. Both field measurements and laboratory experiments have gathered convincing evidence about the importance of volatile organic compounds (VOCs) in enhancing the nucleation and growth of aerosol particles. Numerous and abundant small clusters composed of sulfuric acid or bisulfate ion and organic molecules have been shown to exist in ∼2 nm sized aerosol particles. In particular, kinetic studies indicated the formation of clusters with one H2SO4 and one or two organics being the rate-limiting step. This Account discusses our effort in developing an integrated approach, which involves the laboratory cluster synthesis via electrospray ionization, size and composition analysis via mass spectrometry, photoelectron spectroscopic characterization, and quantum mechanics based theoretical modeling, to investigate the structures, energetics, and thermodynamics of the aerosol prenucleation clusters relevant to NPF. We have been focusing on the clusters formed between H2SO4 or HSO4 – and the organics from oxidation of both biogenic and anthropogenic emissions. We illustrated the significant thermodynamic advantage by involving organic acids in the formation and growth of aerosol clusters. We revealed that the functional groups in the organics play critical roles in promoting NPF process. The enhanced roles were quantified explicitly for specific functional groups, establishing a Molecular Scale that ranks highly hierarchic intermolecular interactions critical to aerosol formation. The different cluster formation pathways, probably mimicking the various polluted industrial environments, that involve cis-pinonic and cis-pinic acids were unveiled as well. Furthermore, one intriguing fundamental phenomenon on the unusual protonation pattern, which violates the gas-phase acidity (proton affinity) prediction, was discovered to be common in sulfuric acid–organic clusters. The mechanism underlying the phenomenon has been rationalized by employing the temperature-dependent experiments of sulfuric acid–formate/halide model clusters, which could explain the hig...

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“…† These observed optimized structures and binding patterns are similar to those of the well-studied complex of sulfuric acid and aromatic carboxylate. 22,66 3.2 Key composition of stable SOA nanoparticles Pyruvic acid dominates synergistic effects. Although the significant thermodynamic advantage of organic acids in the formation and growth of SOA clusters has been reported frequently, 22,32,35 the synergistic effects are discussed here in detail.…”

Section: Resultsmentioning

confidence: 99%