Nuclear Quantum Effects in the Ionic Dissociation Dynamics of HCl on the Water Ice Cluster

Molecules, Journal Year: 2025, Volume and Issue: 30(3), P. 442 - 442

Published: Jan. 21, 2025

Nuclear quantum effects play a significant role in the dissociation dynamics of HCl ions during collisions with (H2O)49 ice cluster. These become particularly important when analyzing proton transfer, tunneling, and zero-point energy contributions process. In this study, we investigate behavior colliding cluster, focusing on influence nuclear transfer mechanism, ionic rates, subsequent solvation dynamics. Through combination classical molecular (MD) ring-polymer (RPMD) simulations, explore how fluctuations proton’s position alter pathway HCl. The inclusion reveals enhanced mobility, leading to differences compared simulations. Our findings indicate that significantly affect dynamics, more readily transferring hydrogen-bond network This study provides insights into mechanical nature hydrogen-bonded systems highlights importance incorporating for accurate modeling processes complex environments.

Language: Английский

Vibrationally Assisted Tunneling through the Bread of a Proton Sandwich─Connections to Dynamic Matching

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 4, 2025

Proton sandwiches are unusual nonclassical carbocations characterized by a five-center, four-electron bonding array which rapidly isomerize to lower energy isomers with three-center, two-electron arrays via hydrogen migration transition states. These reactions suspected involve significant contributions from tunneling, even at relatively high temperatures, where tunneling effects usually minimal. Machine-learning-accelerated ring-polymer, quasiclassical, and classical ab initio molecular dynamics simulations were used investigate the of flavor dynamic matching that involves coupling vibrational modes reactant structure mode an imaginary frequency, how quantum mechanical affects this coupling. nonstatistical quantified analysis momentum in simulations. We show importance for reactivity without amplifies these benefits, can be leveraged generate beneficial momentum.

Language: Английский

Unraveling Reaction Path Bifurcation: Insights Into Electron Movement via Natural Reaction Orbitals

Journal of Computational Chemistry, Journal Year: 2025, Volume and Issue: 46(10)

Published: April 11, 2025

ABSTRACT This study investigates the Beckmann rearrangement of 1‐phenyl‐2‐propanone oxime derivatives, focusing on reaction path bifurcation behavior from perspective electron movement. The previous work reported that electron‐withdrawing substituents drove toward pathway, while electron‐donating favored fragmentation pathway. Through natural orbital (NRO) analysis, this research demonstrates how electrons move at critical branching points, specifically in directions intrinsic coordinate (IRC) and projected vibrational mode associated with behavior. NRO approach, which complements traditional IRC ab initio molecular dynamics methods, not only provides valuable quantitative insights for predicting product distributions but also aids strategic design desired products. These findings extend our understanding mechanisms byproduct formation, offering fresh perspectives complex chemical transformations.

Language: Английский