Effect of ammonia-water complex on decomposition of carbonic acid in troposphere: A quantum chemical investigation

Mallick, Subhasish; Sarkar, Saptarshi; Bandyopadhyay, Biman; Kumar, Pradeep

doi:10.1016/j.comptc.2018.04.005

Cited by 28 publications

(15 citation statements)

References 55 publications

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“…Generally, these processes are usually considered to be catalyzed by amphoteric structures capable of simultaneous proton donation and proton capture, such as water, acids, alcohols or ammonia. [ 21 , 22 , 23 , 24 ] In contrast, we propose a stepwise mechanism in which the acid is deprotonated first, leading to an intermediate ion pair. This ion pair readily undergoes decomposition, recovering the base and forming the corresponding alcohol.…”

Section: Resultsmentioning

confidence: 84%

“…To our notice, this kind of pyridine‐mediated decomposition of a carbonic acid derivative has not been reported before. Generally, these processes are usually considered to be catalyzed by amphoteric structures capable of simultaneous proton donation and proton capture, such as water, acids, alcohols or ammonia [21–24] . In contrast, we propose a stepwise mechanism in which the acid is deprotonated first, leading to an intermediate ion pair.…”

Section: Resultsmentioning

confidence: 90%

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Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence

Garay-Ruiz

Bó

2021

Chemistry A European J

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The heterolytic decomposition of tert‐butyl peroxyformate to tert‐butanol and carbon dioxide, catalyzed by pyridine, is a long‐known example of a reaction whose kinetics are strongly affected by solvent polarity. From DFT and ab initio methods together with the SMD implicit solvation model, an extension on the formerly accepted mechanism is proposed. This novel proposal involves the formation of a carbonic acid ester intermediate and its further decomposition, through an unreported pyridine‐mediated stepwise route. Computed barriers for this mechanism at DLPNO/CCSD(T)‐def2‐TZVP are in excellent agreement with experimental kinetic data across different solvents. Furthermore, the strong relationships between activation energies, geometric parameters in the transition state and the characteristics of the different solvents are also analyzed in depth.

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Section: Resultsmentioning

confidence: 84%

Section: Resultsmentioning

confidence: 90%

Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence

Garay-Ruiz

Bó

2021

Chemistry A European J

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“…The decomposition of carbonic acid could be efficiently promoted by a variety of species, such as water, ammonia, sulfuric acid, organics, and cloud particle surfaces. That could be one reason why isolated H 2 CO 3 has escaped direct detection for a long time [11][12][13][14][15][16][17]. In 1987, Schwarz and co-workers reported the first observation of isolated H 2 CO 3 via neutralization-reionization mass spectrometry of heated ammonium bicarbonate (NH 4 HCO 3 ) vapor [1].…”

Section: Introductionmentioning

confidence: 99%

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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“…[ 24 ] In another example, NH 3 makes the HO + HCl [ 25 ] reaction barrierless, and the rate constant for an NH 3 ‐catalyzed HO + HCl reaction was found to be ~10 3 times higher compared to the reaction assisted by H 2 O. Meanwhile, it was found that, due to a higher relative concentration than ammonia dimer (NH 3 ) 2 , the bifunctional basic catalyst H 3 N···H 2 O in the decomposition of H 2 CO 3 [ 26 ] and the isomerization of CH 3 O [ 24 ] can compete with other catalysts such as H 2 O, (H 2 O) 2 , and NH 3 , which are known to facilitate these reactions. These facts clearly showed that the catalytic effect of NH 3 and H 3 N···H 2 O in modeling the atmospheric hydrogen abstraction reaction of HO 2 + HO 2 → H 2 O 2 + 3 O 2 cannot be neglected.…”

Section: Introductionmentioning

confidence: 99%

Effect of ammonia, ammonia‐water, and sulfuric acid on the HO₂ + HO₂ → H₂O₂ + 3O₂ reaction in troposphere: Competition between stepwise and one‐step mechanisms

Wen

Cao

Zhang

et al. 2020

Int J of Quantum Chemistry

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A detailed theoretical study on the reaction mechanisms for the formations of H 2 O 2 + 3 O 2 from the self-reaction of HO 2 radicals under the effect of NH 3 , H 3 NÁÁÁH 2 O, and H 2 SO 4 catalysts was performed using the CCSD(T)/CBS//M06-2X/ aug-cc-pVTZ method. The rate constant was computed using canonical variational transition state theory (CVT) with small curvature tunneling (SCT). Our results indicate that NH 3-, H 3 NÁÁÁH 2 O-, and H 2 SO 4-catalyzed reactions could proceed through both one-step and stepwise routes. Calculated rate constants show that the catalyzed routes in the presence of the three catalysts all prefer stepwise pathways. Compared to the catalytic efficiency of H 2 O, the efficiencies of NH 3 , H 3 NÁÁÁH 2 O, and H 2 SO 4 are much lower due to their smaller relative concentrations. The present results have provided a definitive example of how basic and acidic catalysts influence the atmospheric reaction of HO 2 + HO 2 ! H 2 O 2 + 3 O 2. These results further encourage one to consider the effects of basic and acidic catalysts on the related atmospheric reactions. Thus, the present investigation should have broad implications in the gas-phase reactions of the atmosphere.

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Effect of ammonia-water complex on decomposition of carbonic acid in troposphere: A quantum chemical investigation

Cited by 28 publications

References 55 publications

Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence

Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence

Stabilizing the Exotic Carbonic Acid by Bisulfate Ion

Effect of ammonia, ammonia‐water, and sulfuric acid on the HO₂ + HO₂ → H₂O₂ + 3O₂ reaction in troposphere: Competition between stepwise and one‐step mechanisms

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Effect of ammonia-water complex on decomposition of carbonic acid in troposphere: A quantum chemical investigation

Cited by 28 publications

References 55 publications

Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence

Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence

Stabilizing the Exotic Carbonic Acid by Bisulfate Ion

Effect of ammonia, ammonia‐water, and sulfuric acid on the HO2 + HO2 → H2O2 + 3O2 reaction in troposphere: Competition between stepwise and one‐step mechanisms

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Effect of ammonia, ammonia‐water, and sulfuric acid on the HO₂ + HO₂ → H₂O₂ + 3O₂ reaction in troposphere: Competition between stepwise and one‐step mechanisms