Tautomeric equilibrium in condensed phases

• Published in: arXiv.org 2020-05
• Main Authors: Grifoni, Emanuele, Piccini, GiovanniMaria, Parrinello, Michele
• Format: Article
• Language: English
• Subjects: Acetone; Aqueous environments; Aqueous solutions; Dynamic structural analysis; Glycine; Molecular dynamics; Protons
• ISSN: 2331-8422
• DOI: 10.48550/arxiv.2005.01658

We present an ab initio molecular dynamics (MD) investigation of the tautomeric equilibrium for aqueous solutions of glycine and acetone at realistic experimental conditions. Metadynamics is used to accelerate proton migration among tautomeric centers. Due to the formation of complex water-ion structures involved the proton dynamics in the aqueous environment, standard enhanced sampling approaches may face severe limitations in providing a general description of the phenomenon. Recently, we developed a set of Collective Variables (CVs) designed to study protons transfer reactions in complex condensed systems [Grifoni et al. PNAS, 2019, 116(10), 4054-4057]. In this work we applied this approach to study proton dissociation dynamics leading to tautomeric interconversion of biologically and chemically relevant prototypical systems, namely glycine and acetone in water. Although relatively simple from a chemical point of view, the results show that even for these small systems complex reaction pathways and non-trivial conversion dynamics are observed. The generality of our method allows obtaining these results without providing any prior information on the dissociation dynamics but only the atomic species that can exchange protons in the process. Our results agree with literature estimates and demonstrate the general applicability of this method in the study of tautomeric reactions.