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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Bond Breaking and Bond Making in Tetraoxygen: Analysis of the O_2(X~3Σ_g~-) + O_2(X~3_g~-)O_4 Reaction Using the Electron Pair Localization Function
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Bond Breaking and Bond Making in Tetraoxygen: Analysis of the O_2(X~3Σ_g~-) + O_2(X~3_g~-)O_4 Reaction Using the Electron Pair Localization Function

机译：四元氧中的键断裂和键形成：使用电子对定位函数分析O_2（X〜3Σ_g〜-）+ O_2（X〜3_g〜-）O_4反应

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We study the nature of the electron pairing at the most important critical points of the singlet potential energysurface of the 2O_2 → O_4reaction and its evolution along the reaction coordinate using electron pairlocalization function (EPLF) [Scemama, A.; Chaquin, P.; Caffarel, M. J. Chem. Phys. 2004, 121, 1725]. Todo that, the 3D topology of the EPLF calculated with quantum Monte Carlo (at both variational and fixed-node-diffusion Monte Carlo levels) using Hartree—Fock, multiconfigurational CASSCF, and explicitlycorrelated trial wave functions is analyzed. At the 04 equilibrium geometry the EPLF analysis reveals fourequivalent covalent bonds and two lone pairs on each oxygen atom. Along the reaction path toward dissociationit is found that the two oxygen—oxygen bonds are not broken simultaneously but sequentially, and then thelone pairs are rearranged. In a more general perspective, the usefulness of the EPLF as a unique tool toanalyze the topology of electron pairing in nontrivial chemical bonding situations as well as to visualize themajor steps involved in chemical reactivity is emphasized. In contrast with most standard schemes to revealelectron localization (atoms in molecules, electron localization function, natural bond orbital, etc.), the newlyintroduced EPLF function gives a direct access to electron pairings in molecules.
机译：我们使用电子对定位功能（EPLF）研究了2O_2→O_4反应的单重态势能面最重要临界点的电子配对性质及其沿反应坐标的演化[Scemama，A .; Chaquin，P .; Caffarel，M.J.Chem。物理2004，121，1725]。为此，分析了使用Hartree-Fock，多配置CASSCF以及明确相关的试验波函数，用量子蒙特卡罗（在变分和固定节点扩散蒙特卡洛水平）计算的EPLF的3D拓扑。在04平衡几何条件下，EPLF分析显示每个氧原子上有四个等价的共价键和两个孤对。沿着朝向解离的反应路径，发现两个氧-氧键不是同时断裂而是依次断裂，然后孤对重新排列。从更普遍的角度来看，强调了EPLF作为分析非配对化学键合情况下电子配对拓扑以及可视化化学反应涉及的主要步骤的独特工具的有用性。与大多数揭示电子定位（分子中的原子，电子定位功能，自然键轨道等）的标准方案相反，新引入的EPLF功能可直接访问分子中的电子对。

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