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How Many Water Molecules Does it Take to Dissociate HCl?

Alba Vargas-Caamal1, Jose Luis Cabellos1, Filiberto Ortiz-Chi2

  • 1Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados, Unidad Mérida, Km 6 Antigua Carretera a Progreso. Apdo. Postal 73, Cordemex, 97310, Mérida, Yuc., México.

Chemistry (Weinheim an Der Bergstrasse, Germany)
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Summary

Dissociation of hydrogen chloride (HCl) in water clusters requires five water molecules when considering entropy, not four. Temperature control is crucial for accurate experimental measurements of HCl dissociation in nanoscopic droplets.

Keywords:
ab initio calculationsdissociationglobal optimizationhydrogen bondsmicrosolvation

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Area of Science:

  • Physical Chemistry
  • Computational Chemistry
  • Chemical Physics

Background:

  • Hydrogen chloride (HCl) dissociation in water clusters is a key process in atmospheric and solution chemistry.
  • Previous experimental studies suggested four water molecules are sufficient for HCl dissociation.

Purpose of the Study:

  • To systematically explore the potential energy surfaces of HCl(H2O)n clusters.
  • To determine the precise number of water molecules required for HCl dissociation, considering electronic and entropic factors.
  • To classify cluster dissociation states using Wiberg bond indices.

Main Methods:

  • Density functional theory (DFT) computations.
  • High-level ab initio calculations.
  • Analysis of Wiberg bond indices to quantify H-Cl bond character.

Main Results:

  • Five water molecules are necessary for HCl dissociation when entropic factors are included, differing from some experimental findings.
  • A quadratic correlation was established between Wiberg bond indices and cluster dissociation states (nondissociated, partially dissociated, fully dissociated).
  • Uncontrolled temperature in experiments can alter measurable properties like dipole moment, affecting the perceived number of water molecules needed for dissociation.

Conclusions:

  • The inclusion of entropic effects is critical for accurately predicting HCl dissociation in water clusters.
  • Temperature control is essential for reproducible and accurate experimental characterization of HCl-water cluster systems.
  • Computational methods provide valuable insights into the complex dissociation dynamics of small clusters.