{"title":"Kinetics of tautomerisation of thiouracils and cognate species at low temperatures: theory versus experiment","authors":"Judith Wurmel, John M Simmie","doi":"10.1039/d4cp04038d","DOIUrl":null,"url":null,"abstract":"Hydrogen-atom tunnelling is an important component in some chemical reactions particularly at low temperatures ≤ 300 K. Recent experiments by Rostkowska et al. [PCCP 2024, 26, 23944–23950] showed that higher energy monomeric conformers of thiouracil and cognate species (thiols) prepared on neon and argon matrices at 3.5 K spontaneously reverted to the lower energy conformer (thiones) presumably by hydrogen-atom quantum mechanical tunnelling. We have shown that these observations can be rationalised by carrying out chemical kinetic calculations employing canonical variational transition state theory with small-curvature and quantised-states tunnelling effects on these systems in the gas-phase. We discount the possibility of adventitious water contaminating the experimental observations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"57 1","pages":""},"PeriodicalIF":2.9000,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4cp04038d","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Hydrogen-atom tunnelling is an important component in some chemical reactions particularly at low temperatures ≤ 300 K. Recent experiments by Rostkowska et al. [PCCP 2024, 26, 23944–23950] showed that higher energy monomeric conformers of thiouracil and cognate species (thiols) prepared on neon and argon matrices at 3.5 K spontaneously reverted to the lower energy conformer (thiones) presumably by hydrogen-atom quantum mechanical tunnelling. We have shown that these observations can be rationalised by carrying out chemical kinetic calculations employing canonical variational transition state theory with small-curvature and quantised-states tunnelling effects on these systems in the gas-phase. We discount the possibility of adventitious water contaminating the experimental observations.
期刊介绍：
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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