Kinetics of tautomerisation of thiouracils and cognate species at low temperatures: theory versus experiment

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-11-20 DOI:10.1039/d4cp04038d

Judith Wurmel, John M Simmie

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.

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硫脲和同系物在低温下的同分异构动力学：理论与实验

Rostkowska 等人最近的实验[PCCP 2024, 26, 23944-23950]表明，在 3.5 K 下，在氖和氩基质上制备的硫脲嘧啶和同系物（硫醇）的高能单体构象会自发地还原为低能构象（亚硫酰），这可能是通过氢原子量子力学隧道效应实现的。我们已经证明，通过采用具有小曲率和定量态隧道效应的典型变异过渡态理论对气相中的这些体系进行化学动力学计算，可以合理地解释这些观察结果。我们排除了实验观测结果受到偶然水污染的可能性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

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.