ArticleChemical science2023
Competing quantum effects in heavy-atom tunnelling through conical intersections.
Article in Chemical science, 2023. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 3 papers.
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Who cites it
3 citing papers in PubMed.
- Nonadiabatic Tunneling in Chemical Reactions.The journal of physical chemistry letters · 2024Review
- Heavy-atom tunnelling in singlet oxygen deactivation predicted by instanton theory with branch-point singularities.Nature communications · 2024Article
- Recovering Marcus Theory Rates and Beyond without the Need for Decoherence Corrections: The Mapping Approach to Surface Hopping.The journal of physical chemistry letters · 2024Article
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Authors and funding
3 authors.
Funding
No grant is acknowledged in the PubMed record.
Abstract
Thermally activated chemical reactions are typically understood in terms of overcoming potential-energy barriers. However, standard rate theories break down in the presence of a conical intersection (CI) because these processes are inherently nonadiabatic, invalidating the Born-Oppenheimer approximation. Moreover, CIs give rise to intricate nuclear quantum effects such as tunnelling and the geometric phase, which are neglected by standard trajectory-based simulations and remain largely unexplored in complex molecular systems. We present new semiclassical transition-state theories based on an extension of golden-rule instanton theory to describe nonadiabatic tunnelling through CIs and thus provide an intuitive picture for the reaction mechanism. We apply the method in conjunction with first-principles electronic-structure calculations to the electron transfer in the bis(methylene)-adamantyl cation. Our study reveals a strong competition between heavy-atom tunnelling and geometric-phase effects.
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Registered trials
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