On the role of interfacial hydrogen bonds in "on-water" catalysis

Abstract

Numerous experiments have demonstrated that many classes of organic reactions exhibit increased reaction rates when performed in heterogeneous water emulsions. Despite enormous practical importance of the observed "on-water" catalytic effect and several mechanistic studies, its microscopic origins remains unclear. In this work, the second generation Car-Parrinello molecular dynamics method is extended to self-consistent charge density-functional based tight-binding in order to study "on-water" catalysis of the Diels-Alder reaction between dimethyl azodicarboxylate and quadricyclane. We find that the stabilization of the transition state by dangling hydrogen bonds exposed at the aqueous interfaces plays a significantly smaller role in "on-water" catalysis than has been suggested previously.

arXiv comment6 pages, 3 figures

References in corpus (7)

• An Efficient and Accurate Car-Parrinello-like Approach to Born-Oppenheimer Molecular Dynamics
• Accurate sampling using Langevin dynamics
• Electronic signature of the instantaneous asymmetry in the first coordination shell of liquid water
• Ab-Initio Molecular Dynamics
• Recent achievements in ab initio modelling of liquid water
• Linear scaling electronic structure calculations and accurate sampling with noisy forces
• Self-consistent field theory based molecular dynamics with linear system-size scaling

Cited by in corpus (6)

• CP2K: An Electronic Structure and Molecular Dynamics Software Package -- Quickstep: Efficient and Accurate Electronic Structure Calculations
• Structure and Dynamics of the Instantaneous Water/Vapor Interface Revisited by Path-Integral and Ab-Initio Molecular Dynamics Simulations
• Towards Electronic Structure-Based Ab-Initio Molecular Dynamics Simulations with Hundreds of Millions of Atoms
• Quantum Ring-Polymer Contraction Method: Including nuclear quantum effects at no additional computational cost in comparison to ab-initio molecular dynamics
• Accurate Sampling with Noisy Forces from Approximate Computing
• Quantum circuit and mapping algorithms for wavepacket dynamics: case study of anharmonic hydrogen bonds in protonated and hydroxide water clusters