用“定向外电场”操纵双原子分子：原子性质的线性相关导致非线性分子响应
Manipulation of Diatomic Molecules with 'Oriented External Electric Fields': Linear Correlations in Atomic Properties Lead to Non-Linear Molecular Responses
摘要：
“定向外电场（OEEF）”已被证明在能够提供从H2存储到分子机器的应用范围内的化学反应、催化和选择性的前所未有的控制方面具有巨大的潜力。我们报告了一项关于OEEF引起分子变化的原子起源的理论研究;了解OEEF诱导的原子和分子性质之间耦合的特征是全面了解强外场对分子结构、稳定性和反应性影响的重要一步。在分子中原子的量子理论（QTAIM）的背景下，我们着重研究了一组同原子（H2，N2，O2，F2，和Cl 2）和异双原子（HF，HCl，CO，和NO）分子在强外电场下的原子和分子（键）性质。结果表明，原子性质（原子电荷和能量，和本地化指数）与场强线性相关，但分子性质（键长，在键临界点的电子密度，键长，和电子离域指数）表现出非线性响应所施加的领域。特别是，在电子密度分布的变化改变的形状和位置的零通量表面，原子体积，原子电子布居，和本地化/离域指数。在分子水平上，分子静电势的形貌和拓扑发生了剧烈的变化。外场也扰动了所研究的化学键的共价-极性-离子特性，标志着电场对化合物的稳定性和反应性的影响。这些发现在分子中原子的量子理论的框架内得到了很好的合理化，并形成了对原型分子（如分子）中这些效应的连贯概念理解。
英文摘要：
'Oriented external electric fields (OEEFs)' have been shown to have great potential in being able to provide unprecedented control of chemical reactions, catalysis and selectivity with applications ranging from H2 storage to molecular machines. We report a theoretical study of the atomic origins of molecular changes due to OEEFs; understanding the characteristics of OEEF-induced couplings between atomic and molecular properties is an important step toward comprehensive understanding of the effects of strong external fields on molecular structure, stability, and reactivity. We focus on the atomic and molecular (bond) properties of a set of homo- (H2, N2, O2, F2, and Cl2) and hetero-diatomic (HF, HCl, CO, and NO) molecules under intense external electric fields in the context of quantum theory of atoms in molecules (QTAIM). It is shown that atomic properties (atomic charges and energies, and localization index) correlate linearly with the field strengths, but molecular properties (bond length, electron density at bond critical point, bond length, and electron delocalization index) exhibit non-linear responses to the imposed fields. In particular, the changes in the electron density distribution alter the shapes and locations of the zero-flux surfaces, atomic volumes, atomic electron population, and localization/delocalization indices. At the molecular level, the topography and topology of the molecular electrostatic potential undergo dramatic changes. The external fields also perturb the covalent-polar-ionic characteristic of the studied chemical bonds, hallmarking the impact of electric fields on the stability and reactivity of chemical compounds. The findings are well-rationalized within the framework of the quantum theory of atoms in molecules and form a coherent conceptual understanding of these effects in prototypical molecules such as diatomics.
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