Non-equilibrium reaction and relaxation dynamics in a strongly interacting explicit solvent: F + CD3CN treated with a parallel multi-state EVB model.
Non-equilibrium reaction and relaxation dynamics in a strongly interacting explicit solvent: F + CD3CN treated with a parallel multi-state EVB model.
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强相互作用显式溶剂中的非平衡反应和弛豫动力学：用并行多态 EVB 模型处理的 F CD3CN。
DOI：
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发表时间：
2014
影响因子：
4.4
通讯作者：
J. Harvey
中科院分区：
文献类型：
--
作者：
D. Glowacki;A. Orr;J. Harvey
我们描述了一个并行化的线性尺度计算框架，实现任意大的多态经验价键（MS-EVB）计算CHARMM和TINKER。使用Hellmann-Feynman关系获得力，给出连续梯度和良好的能量守恒。利用多维高斯耦合元素拟合显式关联耦合团簇理论，我们建立了一个64态MS-EVB模型，旨在研究CD 3CN溶剂中的F + CD 3CN → DF + CD 2CN反应（最近在Dunning等人[Science 347（6221），530（2015）]中报道）。这种方法使我们能够建立一个反应势能面，其平衡的准确性和效率大大超过我们可以实现，否则。我们运行的分子动力学模拟，以检查一系列的可观察到的反应事件之后：能量沉积在新生的反应产物，振动弛豫速率的激发DF在CD 3CN溶剂，平衡功率谱的DF在CD 3CN，和时间相关的光谱位移与新生DF的弛豫。我们的许多结果与时间分辨的实验观察结果吻合良好，为我们的MS-EVB框架在处理溶质和溶质/溶剂相互作用的准确性提供了证据。模拟提供了额外的洞察力，在亚皮秒的时间尺度，很难解决实验的动态。特别是，模拟显示，（紧接着氘提取之后）新生DF发现其自身在两个不同方面处于非平衡状态：（1）它是高度振动激发的，在拉伸中具有约23 kcal mol（-1），以及（2）它的反应后溶剂化环境，其中它尚未与CD 3CN溶剂分子氢键结合，在非相互作用的气相极限和溶液相平衡极限之间。新生DF的振动弛豫导致光谱蓝移，而反应后溶剂化环境的弛豫导致红移。这两个竞争的影响意味着反应后的弛豫曲线是不同的观察时，弗兰克-康登振动激发DF发生在一个微溶剂化环境中最初在平衡。我们的结论，沿着本文提出的理论和并行软件框架，应该更广泛地适用于一系列复杂的反应系统。
We describe a parallelized linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM and TINKER. Forces are obtained using the Hellmann-Feynman relationship, giving continuous gradients, and good energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to explicitly correlated coupled cluster theory, we built a 64-state MS-EVB model designed to study the F + CD3CN → DF + CD2CN reaction in CD3CN solvent (recently reported in Dunning et al. [Science 347(6221), 530 (2015)]). This approach allows us to build a reactive potential energy surface whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We ran molecular dynamics simulations to examine a range of observables which follow in the wake of the reactive event: energy deposition in the nascent reaction products, vibrational relaxation rates of excited DF in CD3CN solvent, equilibrium power spectra of DF in CD3CN, and time dependent spectral shifts associated with relaxation of the nascent DF. Many of our results are in good agreement with time-resolved experimental observations, providing evidence for the accuracy of our MS-EVB framework in treating both the solute and solute/solvent interactions. The simulations provide additional insight into the dynamics at sub-picosecond time scales that are difficult to resolve experimentally. In particular, the simulations show that (immediately following deuterium abstraction) the nascent DF finds itself in a non-equilibrium regime in two different respects: (1) it is highly vibrationally excited, with ∼23 kcal mol(-1) localized in the stretch and (2) its post-reaction solvation environment, in which it is not yet hydrogen-bonded to CD3CN solvent molecules, is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational relaxation of the nascent DF results in a spectral blue shift, while relaxation of the post-reaction solvation environment results in a red shift. These two competing effects mean that the post-reaction relaxation profile is distinct from what is observed when Franck-Condon vibrational excitation of DF occurs within a microsolvation environment initially at equilibrium. Our conclusions, along with the theoretical and parallel software framework presented in this paper, should be more broadly applicable to a range of complex reactive systems.
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影响因子：
1.7
作者：
H. Werner;G. Knizia;F. Manby
通讯作者：
H. Werner;G. Knizia;F. Manby
HO-SO2 中能量重新分配的量子动力学模拟
影响因子：
2.3
作者：
Reed S
通讯作者：
Reed S
影响因子：
15
作者：
Glowacki, David R.;Liang, C. H.;Pilling, Michael J.
通讯作者：
Pilling, Michael J.
氯化溶剂中 Cl 原子与 2,3-二甲基丁-2-烯反应的振动解析动力学
DOI：
10.1039/c2sc21267f
发表时间：
2013
期刊：
Chem. Sci.
影响因子：
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作者：
Abou-Chahine F
通讯作者：
Abou-Chahine F
影响因子：
21.8
作者：
Otto, R.;Brox, J.;Wester, R.
通讯作者：
Wester, R.