Understanding the nature of bonding interactions in the carbonic acid dimers

  • Andy D. Zapata–Escobar
  • Juliana Andrea Murillo–López
  • C. Z. Hadad
  • Albeiro RestrepoEmail author
Original Paper


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.

Graphical Abstract

Carbonic acid dimer, (CA)2, (H2CO3)2, helps explaining 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⋯O–H, C=O⋯C=O, C=O⋯O–C, and C–O⋯O–C. In many cases, the stabilizing hydrogen bonds are of at least the same strength as in the water dimer.


Carbonic acid QTAIM NBOs Hydrogen bonds Bifurcated bonds 



Quantum theory of atoms in molecules.


Bond critical points.


Natural bond orbitals



Financial support for this project by Colciencias via project 111571249844, contract 378–2016 is acknowledged. J.M. acknowledges CONICYT for her postdoctoral Project FONDECYT/Postdoctorado-2015 No. 3150041.

Funding Information

Colciencias, Colombia: Project 111571249844, contract 378–2016. Conicyt, Chile: Fondecyt project, Postdoctorado–2015 No. 3150041.

Supplementary material

894_2018_3907_MOESM1_ESM.pdf (117 kb)
(PDF 117 KB)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Andy D. Zapata–Escobar
    • 1
  • Juliana Andrea Murillo–López
    • 2
  • C. Z. Hadad
    • 1
  • Albeiro Restrepo
    • 1
    Email author
  1. 1.Instituto de QuímicaUniversidad de Antioquia UdeAMedellínColombia
  2. 2.Departamento de Ciencias Químicas, Facultad de Ciencias ExactasUniversidad Andres BelloSantiagoChile

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