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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Thermal and Microcanonical Rates of Unimolecular Reactions from an Energy Diffusion Theory Approach
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Thermal and Microcanonical Rates of Unimolecular Reactions from an Energy Diffusion Theory Approach

机译：基于能量扩散理论方法的单分子反应的热和微规范速率

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摘要

We present an energy diffusion theory approach for computing thermal and microcanonical unimolecular reaction rates by solving the general energy diffusion equation. The solution naturally provides the rates in the diffusion limit for fast reactions and the transition state theory (TST) limit for slow reactions. The reaction rates between the two limits can be easily obtained by solving a one-dimensional Schrodinger-like equation transformed from the diffusion equation. Employing a model system consisting of a set of harmonic oscillators interacting with a heat bath, the thermal rates from the low-temperature TST regime to the high-temperature diffusion regime are calculated to demonstrate their dependence on the size of the molecule. The approach also provides a practical means of obtaining microcanonical rates at considerable savings of computer time compared to trajectory simulations. THe method is applied to the unimolecular dissociation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and its accuracy is demonstrated by comparison with the results from trajectory and Monte Carlo variational transition state calculations.
机译：我们提出了一种能量扩散理论方法，通过求解一般的能量扩散方程来计算热和微规范的单分子反应速率。该解决方案自然为快速反应提供了扩散极限中的速率，为缓慢反应提供了过渡态理论（TST）极限。通过求解从扩散方程式变换的一维类似于薛定inger方程式，可以轻松获得两个极限之间的反应速率。使用由一组与加热浴相互作用的谐波振荡器组成的模型系统，计算从低温TST态到高温扩散态的热速率，以证明它们对分子大小的依赖性。与轨迹模拟相比，该方法还提供了一种实用的方法，可在节省大量计算机时间的情况下获得微规范率。该方法应用于RDX（六氢-1,3,5-三硝基-1,3,5-三嗪）的单分子解离，并通过与轨迹和蒙特卡洛变分过渡态计算的结果进行比较证明了其准确性。

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