Reduced Cost Computation and Exploitation of Accurate Radial Interaction Potentials for Barrier-Less Processes DOI
Luigi Crisci, Bernardo Ballotta, Marco Mendolicchio

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(21), P. 9435 - 9445

Published: Nov. 1, 2024

Barrier-less steps are typical of radical and ionic reactions in the gas-phase, which often take place extreme environments such as combustion reactors operating at very high temperatures or interstellar medium, characterized by ultralow pressures. The difficulty experimental studies conditions mimicking these suggests that computational approaches can provide a valuable support. In this connection, most advanced treatments processes framework transition state theory able to deliver accurate kinetic parameters provided underlying potential energy surface is sufficiently accurate. Since requires balanced treatment static dynamic correlation (which play different roles regions), sophisticated expensive quantum chemical required. One effective solution problem offered computation one-dimensional radial potentials, then used correct results Monte Carlo sampling performed cheaper approaches. paper, we will show that, for large panel barrier-less reaction steps, ruled

Language: Английский

Predicting Rate Constants of Alkane Cracking Reactions Using Machine Learning DOI
Yu Zhang, Min Xia, Hongwei Song

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(12), P. 2383 - 2392

Published: March 13, 2024

Calculating the thermal rate constants of elementary combustion reactions is great importance in theoretical chemistry. Machine learning has become a powerful, data-driven method for predicting nowadays. Recently, molecular similarity combined with topological indices were proposed to represent hydrogen abstraction alkane [

Language: Английский

Citations

5
Reconciling Accuracy and Feasibility for Barrierless Reaction Steps by the PCS/DDCI/MC-PDFT Protocol: Methane and Ethylene Dissociations as Case Studies DOI
Luigi Crisci, Vincenzo Barone

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 17, 2024

Several enhancements have been introduced into state-of-the-art computational protocols for the treatment of barrierless reaction steps in framework variable coordinate variational transition state theory. The first step is synergistic integration Iterative Difference Dedicated Configuration Interaction (I-DDCI) and Pisa Composite Scheme, which defines a reduced cost, yet very accurate, workflow. This approach provides near black box tool obtaining 1D reference potentials. Then, general strategy has devised tuning level theory used Monte Carlo (MC) sampling, employing Multiconfiguration Pair Density Functional Theory (MC-PDFT) with dynamically adjusted Hartree-Fock exchange. Concurrently, partial geometry optimizations during MC simulations account coupling between coordinates conserved modes. protocol closely approaches full size consistency yields highly accurate results, several test computations suggesting rapid convergence I-DDCI correction basis set dimensions. capabilities new platform are illustrated by two case studies (the hydrogen dissociation from CH

Language: Английский

Citations

2
Reduced Cost Computation and Exploitation of Accurate Radial Interaction Potentials for Barrier-Less Processes DOI
Luigi Crisci, Bernardo Ballotta, Marco Mendolicchio

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(21), P. 9435 - 9445

Published: Nov. 1, 2024

Barrier-less steps are typical of radical and ionic reactions in the gas-phase, which often take place extreme environments such as combustion reactors operating at very high temperatures or interstellar medium, characterized by ultralow pressures. The difficulty experimental studies conditions mimicking these suggests that computational approaches can provide a valuable support. In this connection, most advanced treatments processes framework transition state theory able to deliver accurate kinetic parameters provided underlying potential energy surface is sufficiently accurate. Since requires balanced treatment static dynamic correlation (which play different roles regions), sophisticated expensive quantum chemical required. One effective solution problem offered computation one-dimensional radial potentials, then used correct results Monte Carlo sampling performed cheaper approaches. paper, we will show that, for large panel barrier-less reaction steps, ruled

Language: Английский

Citations

0