HCl solvation at the surface and within methanol clusters/nanoparticles II: Evidence for molecular wires


Uras-Aytemiz N., Devlin J. P. , Sadlej J., Buch V.

JOURNAL OF PHYSICAL CHEMISTRY B, vol.110, no.43, pp.21751-21763, 2006 (Journal Indexed in SCI) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 110 Issue: 43
  • Publication Date: 2006
  • Doi Number: 10.1021/jp062753z
  • Title of Journal : JOURNAL OF PHYSICAL CHEMISTRY B
  • Page Numbers: pp.21751-21763

Abstract

Condensed-phase solvation of HCl on and within methanol nanoparticles was investigated by Fourier transform infrared ( FTIR) spectroscopy, on-the-fly molecular dynamics as implemented in the density functional code Quickstep ( which is part of the CP2K package), and ab initio calculations. Adsorption and solvation stages are identified and assigned with the help of calculated infrared spectra obtained from the simulations. The results have been further checked with MP2-level ab initio calculations. The range of acid solvation states extends from the single-coordinated slightly stretched HCl to proton-sharing with Zundel-like methanol (OH+...X-)-H-... states, and finally to MeOH2+...Cl- units with full proton transfer. Furthermore, once the proton moves to methanol, it is mobilized along methanol molecular chains. Since the proton dynamics reflects the evolving local structures, the "proton" spectra display broad bands usually with underlying continua.