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Double proton transfer in hydrated formic acid dimer: Interplay of spatial symmetry and solvent-generated force on reactivity
JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift)
 
ID 4646870
Author(s) Töpfer, Kai; Käser, Silvan; Meuwly, Markus
Author(s) at UniBasel Meuwly, Markus
Year 2022
Title Double proton transfer in hydrated formic acid dimer: Interplay of spatial symmetry and solvent-generated force on reactivity
Journal Physical Chemistry Chemical Physics
Volume 24
Number 22
Pages / Article-Number 13869-13882
Mesh terms Flavin-Adenine Dinucleotide; Formates, chemistry; Protons; Solvents
Abstract The double proton transfer (DPT) reaction in the hydrated formic acid dimer (FAD) is investigated at molecular-level detail. For this, a global and reactive machine learned (ML) potential energy surface (PES) is developed to run extensive (more than 100 ns) mixed ML/MM molecular dynamics (MD) simulations in explicit molecular mechanics (MM) solvent at MP2-quality for the solute. Simulations with fixed - as in a conventional empirical force field - and conformationally fluctuating - as available from the ML-based PES - charge models for FAD show a significant impact on the competition between DPT and dissociation of FAD into two formic acid monomers. With increasing temperature the barrier height for DPT in solution changes by about 10% (∼1 kcal mol-1) between 300 K and 600 K. The rate for DPT is largest, ∼1 ns-1, at 350 K and decreases for higher temperatures due to destabilisation and increased probability for dissociation of FAD. The water solvent is found to promote the first proton transfer by exerting a favourable solvent-induced Coulomb force along the O-H⋯O hydrogen bond whereas the second proton transfer is significantly controlled by the O-O separation and other conformational degrees of freedom. Double proton transfer in hydrated FAD is found to involve a subtle interplay and balance between structural and electrostatic factors.
Publisher Royal Society of Chemistry
ISSN/ISBN 1463-9076 ; 1463-9084
edoc-URL https://edoc.unibas.ch/89225/
Full Text on edoc Available
Digital Object Identifier DOI 10.1039/d2cp01583h
PubMed ID http://www.ncbi.nlm.nih.gov/pubmed/35620978
ISI-Number 000800486600001
Document type (ISI) Journal Article
 
   

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04/05/2024