Electric Dipole Moments of Nitric Acid-Water Complexes Measured by Cluster Beam Deflection

Moro, Ramiro; Heinrich, Jonathon; Kresin, Vladimir Z.

doi:10.1063/1.3275689

Cited by 5 publications

(7 citation statements)

References 17 publications

(29 reference statements)

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“…This information is of great fundamental interest in solvation chemistry and has been pursuit for many years, e.g., for hydrogen halides, namely HCl, in water that served as the benchmark system. It was investigated, e.g., by spectroscopy in ice, , in clusters, , in helium nanodroplets, by dipole moment deflection, , and by other methods. Further examples, where acidic dissolution in water clusters was investigated, are nitric acid , and sulfuric acid .…”

Section: Resultsmentioning

confidence: 99%

Effect of Hydration on Electron Attachment to Methanesulfonic Acid Clusters

et al. 2022

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We report an experimental and computational study of the electron-induced chemistry of methanesulfonic acid (MSA, MeSO3H) in clusters. We combine the mass spectra after the 70 eV electron ionization with the negative ion spectra after electron attachment (EA) at low electron energies of 0–15 eV of the MSA molecule, small MSA clusters, and microhydrated MSA clusters to reveal the solvation effects. The MSA/He coexpansion only generates small MSA clusters with up to four molecules, but adding water substantially hydrates the MSA clusters, resulting in clusters composed of 1–2 MSA molecules accompanied by quite a few water molecules. The clustering strongly suppresses the fragmentation of the MSA molecules upon both the positive ionization and EA. The electron-energy-dependent ion yield for different negative ions is measured. For the MSA molecule and pure MSA clusters, EA leads to an H-abstraction yielding MeSO3 –. It proceeds efficiently at low electron energies below 2 eV with a shoulder at 3–4 eV and a broad, almost 2 orders of magnitude weaker, peak around 8 eV. The hydrated (H2O) n MeSO3 – ions with n ≤ 3 exhibit only a broad peak around 7 eV similar to EA of pure water clusters. Thus, for the small clusters, the electron attachment and hydrogen abstraction from water occur. On the other hand, the larger clusters with n > 4 display a peak below 2 eV, which quickly dominates the spectrum with increasing n. This peak is related to the formation of the H3O+·MeSO3 – ion pair upon hydration and subsequent dipole-supported electron attachment followed by the hydronium neutralization and H3O• radical dissociation. The size-resolved experimental data indicate that the ionic dissociation of MSA starts to occur in the neutral MeSO3H(H2O) N clusters with about four water molecules.

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Section: Resultsmentioning

confidence: 99%

Effect of Hydration on Electron Attachment to Methanesulfonic Acid Clusters

et al. 2022

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“…It should be mentioned that the measurements of the cluster dipole moments by deflection in electric fields did not show any significant increase of the dipole moment at n = 4 or 5 . Therefore, an alternative interpretation may involve ion–molecule reactions in the cluster after ionization.…”

mentioning

confidence: 88%

Nucleation of Mixed Nitric Acid–Water Ice Nanoparticles in Molecular Beams that Starts with a HNO₃ Molecule

Lengyel

Pysanenko

Kočišek

et al. 2012

J. Phys. Chem. Lett.

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Mixed (HNO3)m(H2O)n clusters generated in supersonic expansion of nitric acid vapor are investigated in two different experiments, (1) time-of-flight mass spectrometry after electron ionization and (2) Na doping and photoionization. This combination of complementary methods reveals that only clusters containing at least one acid molecule are generated, that is, the acid molecule serves as the nucleation center in the expansion. The experiments also suggest that at least four water molecules are needed for HNO3 acidic dissociation. The clusters are undoubtedly generated, as proved by electron ionization; however, they are not detected by the Na doping due to a fast charge-transfer reaction between the Na atom and HNO3. This points to limitations of the Na doping recently advocated as a general method for atmospheric aerosol detection. On the other hand, the combination of the two methods introduces a tool for detecting molecules with sizable electron affinity in clusters.

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“…Partial transfer of the HNO 3 proton to a neighboring water molecule was calculated and experimentally confirmed by microwave spectroscopy in the nitric acid trihydrate complex . Surprisingly, the measurements of the cluster dipole moments by deflection in electric fields did not exhibit any significant increase of the dipole moment at N = 4 or 5 . For (HNO 3 ) M (H 2 O) N with M = 2 and 3, the formation of the (H 3 O + ⋯

N {normalO}_{3}^{-}

) ion‐pair structure was predicted to be energetically preferred for 3 and 4 water molecules …”

Section: Examples Of Atmospheric Cluster Studiesmentioning

confidence: 88%

“…204 Surprisingly, the measurements of the cluster dipole moments by deflection in electric fields did not exhibit any significant increase of the dipole moment at N = 4 or 5. 205 For (HNO 3 ) M (H 2 O) N with M = 2 and 3, the formation of the (H 3 O + ⋯NO À 3 ) ion-pair structure was predicted to be energetically preferred for 3 and 4 water molecules. 112…”

Section: Acid Dissociationmentioning

confidence: 99%

Mass spectrometry of aerosol particle analogues in molecular beam experiments

Fárnı́k

Lengyel

2017

Mass Spectrometry Reviews

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Nanometer-size particles such as ultrafine aerosol particles, ice nanoparticles, water nanodroplets, etc, play an important, however, not yet fully understood role in the atmospheric chemistry and physics. These species are often composed of water with admixture of other atmospherically relevant molecules. To mimic and investigate such particles in laboratory experiments, mixed water clusters with atmospherically relevant molecules can be generated in molecular beams and studied by various mass spectrometric methods. The present review demonstrates that such experiments can provide unprecedented details of reaction mechanisms, and detailed insight into the photon-, electron-, and ion-induced processes relevant to the atmospheric chemistry. After a brief outline of the molecular beam preparation, cluster properties, and ionization methods, we focus on the mixed clusters with various atmospheric molecules, such as hydrated sulfuric acid and nitric acid clusters, N O and halogen-containing molecules with water. A special attention is paid to their reactivity and solvent effects of water molecules on the observed processes.

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Electric Dipole Moments of Nitric Acid-Water Complexes Measured by Cluster Beam Deflection

Cited by 5 publications

References 17 publications

Effect of Hydration on Electron Attachment to Methanesulfonic Acid Clusters

Effect of Hydration on Electron Attachment to Methanesulfonic Acid Clusters

Nucleation of Mixed Nitric Acid–Water Ice Nanoparticles in Molecular Beams that Starts with a HNO₃ Molecule

Mass spectrometry of aerosol particle analogues in molecular beam experiments

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Electric Dipole Moments of Nitric Acid-Water Complexes Measured by Cluster Beam Deflection

Cited by 5 publications

References 17 publications

Effect of Hydration on Electron Attachment to Methanesulfonic Acid Clusters

Effect of Hydration on Electron Attachment to Methanesulfonic Acid Clusters

Nucleation of Mixed Nitric Acid–Water Ice Nanoparticles in Molecular Beams that Starts with a HNO3 Molecule

Mass spectrometry of aerosol particle analogues in molecular beam experiments

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Product

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Nucleation of Mixed Nitric Acid–Water Ice Nanoparticles in Molecular Beams that Starts with a HNO₃ Molecule