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First Principles and Experimental 1 H NMR Signatures of Solvated Ions: The Case of HCl(aq)
Author(s) -
Murakhtina Tatiana,
Heuft Jasper,
Meijer Evert Jan,
Sebastiani Daniel
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200600385
Subject(s) - chemistry , solvation , solvation shell , chemical shift , aqueous solution , ion , molecule , hydrogen bond , nmr spectra database , ab initio , ab initio quantum chemistry methods , molecular dynamics , computational chemistry , chlorine , nuclear magnetic resonance spectroscopy , chloride , spectral line , stereochemistry , organic chemistry , physics , astronomy
A combined experimental and ab initio study is presented of the 1 H NMR chemical shift distribution of aqueous hydrogen chloride solution as a function of acid concentration, based on Car–Parrinello molecular dynamics simulations and fully periodic NMR chemical‐shift calculations. The agreement of computed and experimental spectra is very good. From first‐principles calculations, we can show that the individual contributions of Eigen and Zundel ions, regular water molecules, and the chlorine solvation shell to the NMR line are very distinct and almost independent of the acid concentration. From the computed instantaneous NMR distributions, it is further possible to characterize the average variation in hydrogen‐bond strength of the different complexes.