Vibrationally Assisted Tunneling through the Bread of a Proton Sandwich─Connections to Dynamic Matching DOI
Yusef Ahmed, Gabriel dos Passos Gomes, Dean J. Tantillo

et al.

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

Determining Rate Coefficients for the 11-Atom Reaction via Ring Polymer Molecular Dynamics Based on a 27-Dimensional Potential Energy Surface: The Reaction between anti-CH3CHOO and H2O DOI
Lijie Liu, Yanlin Fu, Hao Wu

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 460 - 467

Published: Jan. 1, 2025

Criegee intermediates (CIs) are potentially significant oxidants and a major source of OH radicals in the troposphere. The

Language: Английский

Citations

1
Nuclear Quantum Effects in the Ionic Dissociation Dynamics of HCl on the Water Ice Cluster DOI Creative Commons
Tatsuhiro Murakami,

Hinami Ueno,

Yuya Kikuma

et al.

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

Citations

0
Vibrationally Assisted Tunneling through the Bread of a Proton Sandwich─Connections to Dynamic Matching DOI
Yusef Ahmed, Gabriel dos Passos Gomes, Dean J. Tantillo

et al.

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

Citations

0