2009/09/29 by S. a Beccara, Giovanni Garberoglio, Beccara, S. a +8
Biochemistry, Genetics and Molecular Biology · Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Advanced Physical and Chemical Molecular Interactions #Biomolecules (q-bio.BM) #Chemical Physics (physics.chem-ph) #FOS: Biological sciences #FOS: Physical sciences #Mesoscale and Nanoscale Physics (cond-mat.mes-hall) #Quantum Mechanics and Applications #Soft Condensed Matter (cond-mat.soft) #cond-mat.mes-hall #cond-mat.soft #physics.chem-ph #q-bio.BM
paper · pdf · doi:10.48550/arxiv.0909.5381
4 pages, 4 figures
arxiv created 2009/09/29 · openalex publication_date 2009/09/29 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
We introduce a framework to investigate ab-initio the dynamics of rare thermally activated reactions. The electronic degrees of freedom are described at the quantum-mechanical level in the Born-Oppenheimer approximation, while the nuclear degrees of freedom are coupled to a thermal bath, through a Langevin equation. This method is based on the path integral representation for the stochastic dynamics and yields the time evolution of both nuclear and electronic degrees of freedom, along the most probable reaction pathways, without spending computational time to explore metastable states. This approach is very efficient and allows to study thermally activated reactions which cannot be simulated using ab-initio molecular dynamics techniques. As a first illustrative application, we characterize the dominant pathway in the cyclobutene to butadiene reaction.