Revisiting the reaction energetics of the CH3O˙ + O2 (3Σ−) reaction: the crucial role of post-CCSD(T) corrections

文献信息

发布日期 2019-02-27
DOI 10.1039/C8CP07536K
影响因子 3.676
作者

Subhasish Mallick, Amit Kumar, Pradeep Kumar


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摘要

The CH3O˙ + O2 reaction has been studied by means of high level ab initio calculations to predict the reaction energy and barrier height with chemical accuracy. We have employed post-CCSD(T) corrections in terms of partial quadratic excitations at the coupled cluster level, along with relativistic, core, spin–orbit and diagonal Born–Oppenheimer corrections, to estimate the barrier height and energetics for the title reaction. After including all the corrections, the reaction energy and barrier height were found to be −26.86 and 2.59 kcal mol−1, respectively, which is in good agreement with the corresponding experimentally derived values. Using this information, we have also calculated the rate constants for the title reaction employing transition state theory (TST) in conjunction with zero curvature tunneling (ZCT) within a temperature range of 250 to 900 K.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

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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