Understanding the nature of bonding interactions in the carbonic acid dimers

Andy D. Zapata–Escobar, Juliana Andrea Murillo–López, C. Z. Hadad, Albeiro Restrepo

Resultado de la investigación: Article

Resumen

Carbonic acid dimer, (CA)2, (H2CO3)2, helps to explain the existence of this acid as a stable species, different to a simple sum between carbon dioxide and water. Five distinct, well characterized types of intermolecular interactions contribute to the stabilization of the dimers, namely, C=O⋯H–O, H–O⋯H–O, C=O⋯C=O, C=O⋯O–H, and C–O⋯O–H. In many cases, the stabilizing hydrogen bonds are of at least the same strength as in the water dimer. We dissect the nature of intermolecular interactions and assess their influence on stability. For a set of 40 (H2CO3)2 isomers, C=O⋯H–O hydrogen bonds between the carbonyl oxygen in one CA molecule and the acidic hydrogen in the hydroxyl group at a second CA molecule are the major stabilizing factors because they exhibit the shortest interaction distances, the largest orbital interaction energies, and the largest accumulation of electron densities around the corresponding bond critical points. In most cases, these are closed-shell hydrogen bonds, however, in a few instances, some covalent character is induced. Bifurcated hydrogen bonds are a common occurrence in the dimers of carbonic acid, resulting in a complex picture with multiple orbital interactions of various strengths. Two anti–anti monomers interacting via the strongest C=O⋯H–O hydrogen bonds are the ingredients for the formation of the lowest energy dimers. [Figure not available: see fulltext.]

Idioma originalEnglish
Número de artículo20
PublicaciónJournal of Molecular Modeling
Volumen25
N.º1
DOI
EstadoPublished - 1 ene 2019
Publicado de forma externa

Huella dactilar

Carbonic Acid
carbonic acid
Dimers
dimers
Hydrogen bonds
Acids
hydrogen bonds
interactions
orbitals
Molecules
Water
ingredients
Carbon Dioxide
Isomers
Hydroxyl Radical
water
Carrier concentration
carbon dioxide
molecules
Hydrogen

ASJC Scopus subject areas

  • Catalysis
  • Computer Science Applications
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Computational Theory and Mathematics
  • Inorganic Chemistry

Citar esto

Zapata–Escobar, A. D., Murillo–López, J. A., Hadad, C. Z., & Restrepo, A. (2019). Understanding the nature of bonding interactions in the carbonic acid dimers. Journal of Molecular Modeling, 25(1), [20]. https://doi.org/10.1007/s00894-018-3907-1
Zapata–Escobar, Andy D. ; Murillo–López, Juliana Andrea ; Hadad, C. Z. ; Restrepo, Albeiro. / Understanding the nature of bonding interactions in the carbonic acid dimers. En: Journal of Molecular Modeling. 2019 ; Vol. 25, N.º 1.
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abstract = "Carbonic acid dimer, (CA)2, (H2CO3)2, helps to explain the existence of this acid as a stable species, different to a simple sum between carbon dioxide and water. Five distinct, well characterized types of intermolecular interactions contribute to the stabilization of the dimers, namely, C=O⋯H–O, H–O⋯H–O, C=O⋯C=O, C=O⋯O–H, and C–O⋯O–H. In many cases, the stabilizing hydrogen bonds are of at least the same strength as in the water dimer. We dissect the nature of intermolecular interactions and assess their influence on stability. For a set of 40 (H2CO3)2 isomers, C=O⋯H–O hydrogen bonds between the carbonyl oxygen in one CA molecule and the acidic hydrogen in the hydroxyl group at a second CA molecule are the major stabilizing factors because they exhibit the shortest interaction distances, the largest orbital interaction energies, and the largest accumulation of electron densities around the corresponding bond critical points. In most cases, these are closed-shell hydrogen bonds, however, in a few instances, some covalent character is induced. Bifurcated hydrogen bonds are a common occurrence in the dimers of carbonic acid, resulting in a complex picture with multiple orbital interactions of various strengths. Two anti–anti monomers interacting via the strongest C=O⋯H–O hydrogen bonds are the ingredients for the formation of the lowest energy dimers. [Figure not available: see fulltext.]",
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Zapata–Escobar, AD, Murillo–López, JA, Hadad, CZ & Restrepo, A 2019, 'Understanding the nature of bonding interactions in the carbonic acid dimers', Journal of Molecular Modeling, vol. 25, n.º 1, 20. https://doi.org/10.1007/s00894-018-3907-1

Understanding the nature of bonding interactions in the carbonic acid dimers. / Zapata–Escobar, Andy D.; Murillo–López, Juliana Andrea; Hadad, C. Z.; Restrepo, Albeiro.

En: Journal of Molecular Modeling, Vol. 25, N.º 1, 20, 01.01.2019.

Resultado de la investigación: Article

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AU - Murillo–López, Juliana Andrea

AU - Hadad, C. Z.

AU - Restrepo, Albeiro

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Carbonic acid dimer, (CA)2, (H2CO3)2, helps to explain the existence of this acid as a stable species, different to a simple sum between carbon dioxide and water. Five distinct, well characterized types of intermolecular interactions contribute to the stabilization of the dimers, namely, C=O⋯H–O, H–O⋯H–O, C=O⋯C=O, C=O⋯O–H, and C–O⋯O–H. In many cases, the stabilizing hydrogen bonds are of at least the same strength as in the water dimer. We dissect the nature of intermolecular interactions and assess their influence on stability. For a set of 40 (H2CO3)2 isomers, C=O⋯H–O hydrogen bonds between the carbonyl oxygen in one CA molecule and the acidic hydrogen in the hydroxyl group at a second CA molecule are the major stabilizing factors because they exhibit the shortest interaction distances, the largest orbital interaction energies, and the largest accumulation of electron densities around the corresponding bond critical points. In most cases, these are closed-shell hydrogen bonds, however, in a few instances, some covalent character is induced. Bifurcated hydrogen bonds are a common occurrence in the dimers of carbonic acid, resulting in a complex picture with multiple orbital interactions of various strengths. Two anti–anti monomers interacting via the strongest C=O⋯H–O hydrogen bonds are the ingredients for the formation of the lowest energy dimers. [Figure not available: see fulltext.]

AB - Carbonic acid dimer, (CA)2, (H2CO3)2, helps to explain the existence of this acid as a stable species, different to a simple sum between carbon dioxide and water. Five distinct, well characterized types of intermolecular interactions contribute to the stabilization of the dimers, namely, C=O⋯H–O, H–O⋯H–O, C=O⋯C=O, C=O⋯O–H, and C–O⋯O–H. In many cases, the stabilizing hydrogen bonds are of at least the same strength as in the water dimer. We dissect the nature of intermolecular interactions and assess their influence on stability. For a set of 40 (H2CO3)2 isomers, C=O⋯H–O hydrogen bonds between the carbonyl oxygen in one CA molecule and the acidic hydrogen in the hydroxyl group at a second CA molecule are the major stabilizing factors because they exhibit the shortest interaction distances, the largest orbital interaction energies, and the largest accumulation of electron densities around the corresponding bond critical points. In most cases, these are closed-shell hydrogen bonds, however, in a few instances, some covalent character is induced. Bifurcated hydrogen bonds are a common occurrence in the dimers of carbonic acid, resulting in a complex picture with multiple orbital interactions of various strengths. Two anti–anti monomers interacting via the strongest C=O⋯H–O hydrogen bonds are the ingredients for the formation of the lowest energy dimers. [Figure not available: see fulltext.]

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