First Principles and Experimental 1H NMR Signatures of Solvated Ions: The Case of HCl(aq)

✍ Scribed by Tatiana Murakhtina; Jasper Heuft; Evert Jan Meijer; Daniel Sebastiani

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 187 KB
• Volume: 7
• Category: Article
• ISSN: 1439-4235
• DOI: 10.1002/cphc.200600385

✦ Synopsis

Abstract

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.