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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electronic Interactions in Aryne Biradicals. Ab Initio Calculations of the Structures, Thermochemical Properties, and Singlet-Triplet Splittings of the Didehydronaphthalenes
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Electronic Interactions in Aryne Biradicals. Ab Initio Calculations of the Structures, Thermochemical Properties, and Singlet-Triplet Splittings of the Didehydronaphthalenes

机译：Aryne Biradicals中的电子相互作用。从头算计算二氢化萘的结构，热化学性质和单重-三重分裂

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摘要

Structural and energetic properties for the lowest energy singlet and triplet states of the 10 didehydronaphthalene isomers are predicted using density functional and multireference second-order perturbation theories. These levels of theory offer excellent agreement with known heats of formation for three singlet isomers when appropriate isodesmic equations are used for prediction. Singlet-triplet splittings and biradical stabilization energies are examined to gain insight into the degree of interaction between the biradical centers. This interaction operates via three distinct mechanisms, namely, through space (overlap), through σ-bonds, and through π-bonds, in order of increasing distance over which quantitative impact is predicted. The first two effects are especially sensitive to the relative orientations of the biradical centers and the shape of the molecular framework that joins them. Simpler models are examined for their utility in predicting singlet-triplet splittings; proton hyperfine splittings in antecedent monoradicals are the best predictors of biradical-state energy splittings.
机译：使用密度泛函和多参考二级扰动理论预测了10种二氢萘异构体的最低能量单重态和三重态的结构和能量性质。当使用适当的等渗方程进行预测时，这些理论水平与三种单线态异构体的已知形成热提供了极好的一致性。检查单重态-三重态分裂和双自由基稳定能，以深入了解双自由基中心之间的相互作用程度。这种相互作用通过三种不同的机制进行操作，即通过空间（重叠），通过σ键和通过π键，顺序是距离的增加，在此距离上可以预测到定量影响。前两个效应对双自由基中心的相对取向和连接它们的分子框架的形状特别敏感。检查了更简单的模型在预测单重态-三重态分裂中的效用;先前的单自由基中的质子超精细分裂是双自由基态能量分裂的最佳预测因子。

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